Depending on your particular situation, you may be interested in technologies
on one or the other end of the Technology Readiness scale, mentioned in a
previous post.
In this post, we will describe a strategy for identifying technologies toward the beginning of the scale, i.e., paper concepts, bench scale developments, and, possibly, pilot scale efforts.
The strategy requires a significant amount of work to be effective. In a nutshell, it is …
Google®
Browse
Sort
In other words, enter a Google® search string, browse at least 10 pages of results, save the items you think may be useful, then scan the resulting abstracts and sort them into the appropriate Technology Readiness category.
Two useful Google® search strings you can use are …
desulfurization proposal
… and …
department of energy desulfurization
Below are the results of this search, with my COMMENT after each item indicating where I think it would fit on the Technology Readiness scale.
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Technical Proposal for Desulfurization on 300 Cubic Meter Biogas
Part 1: Project profiles
According to the need to design to build a set of desulfurization equipment for handling capacity of 300 m3 / h biogas desulfurization equipment.
Desulfurization design principles:
A1 use advanced, mature, reliable technology and equipment.
A2 process scheme can fully meet the requirements of national standards for civil usage of biogas.
A3 guarantee the rationality of the process and long-term stability of operation.
A4 practical and conservation investment combined.
A5. Customers actual biogas dosage of 300Nm3 / h, hydrogen sulfide content 7000PPM / Nm3, because the higher amount of hydrogen sulfide, so use processing capacity of 300Nm3 / h methane or biogas desulfurization system.
Part 2: Desulfurization equipment Process Description
1. desulfurization system process:
At present, the methane gas desulfurization process basically is divided into two types: one for dry desulfurization, and the other for wet FGD. Dry FGD is divided into iron oxide desulfurization and activated carbon desulfurization. The common problem of the two kinds of dry desulfurization methods is that the sulfur capacity of desulfurization agent is too small, less adjustment of the operation load, and difficulty of recycling of desulfurizing agent.
2. Our proposed biogas desulfurization method is Wet desulfurization method (COS method), with advantages of: stable operation performance, high desulfurizing efficiency, and lower consumption of raw materials.
With the rapid development of science and technology in recent years, we have achieved significant development in the areas of desulfurization, the desulfurizing upgrading speed quickly. The CoS new family of efficient desulfurization catalyst is developed to meet the demand of the current market demand, the newly developed high-tech innovations, technical performance has reached international advanced level. Based on extensive research of the desulfurization agent market, a detailed analysis of the advantages and disadvantages of the desulfurizer at home and abroad, collecting opinions from customers, according to the plant changes in the level of sulfur content in the actual situation and in the biogas, and constantly improve the product formulation and use of technology, developed a the CoS new highly efficient desulfurization catalyst, it has outstanding advantages of low consumption, low cost. The CoS efficient desulfurization catalyst is a kind of dual control of metal phthalocyanine cyanide cobalt compounds, a desulfurization catalyst of high activity, mainly used for liquid phase catalytic oxidation desulfurization decyanation, the desulfurization efficiency of 99% or more, decyanation efficiency of 98%, so more than 60% of the organic sulfur can be removed. And good technical, economic and social benefits have been significantly achieved for the end users. The CoS efficient desulfurization catalyst, a new generation of desulfurization catalyst produced/developed though further improvement of the active components and optimization of the production process, when compared with former catalyst, has the advantages of simplicity in production, high desulfurization efficiency, high sulfur capacity, high adoption of biogas, clear regeneration solution, less block to equipments towers, easy sulfur removal, low consumption and low cost. It is the first option as efficient desulfurization catalyst in the desulfurization of fertilizer, coking and other types of bio gas desulfurization process.
3. The physical and chemical properties of the catalyst:
Appearance: blue-gray powder.
Density: less than or equal 0.96g / cc
Main ingredients: 92%
Water insoluble matter: less than or equal 3.0% have a good solubility in water or an alkaline aqueous solution.
Soda ash in aqueous solution was sky blue, pale green in ammonia.
Does not decompose in the acid medium, good chemical stability. The catalyst itself is non-corrosive, non-toxic.
4. the usage and characteristics:
CoS desulfurization catalyst can be widely used for various types of desulfurization for gases as: biogas, producer gas, city coal gas desulfurization process gas wet air oxidation desulfurization. The product is of non-toxic, non-corrosive, non-polluting. Whether in the normal temperature and pressure or pressured conditions, regardless of ammonia or soda ash absorbent, the catalyst is able to maintain the stability of the desulfurization efficiency, when used or without additional co-catalyst. Its pre-activation process is simple, time is short, and hydrogen sulfide removal rate of up to 99%, organic sulfur removal rate of up to 60%, hydrogen cyanide removal rate of up to 98% The product has the characters of high activity, long operation life, high anti-cyanide hydrogen poisoning, it can dissolve deposition of sulfur and attached sulfur in the desulfurization unit within the system.
So it can also clean system equipment. The advantages of high sulfurization capacity, regeneration, larger suspended sulfur particles ( which is conducive to separation, do not block the tower, the removal of sulfur high purity, non-corrosive, it does not produce accumulation in the desulfurization unit without the problem of waste water treatment, no environmental pollution, can reduce the resistance of the system, reducing energy consumption, so that the equipment to extend the maintenance period, the apparent decline in the cost of desulfurization. When in operation, the process is very simple without need to change the original process, no additional equipment and very convenient to replace the old desulfurizing equipments and process.
a) On the use of devices in the liquid phase catalysis, the use of sulfur gas desulfurization:
(1), the preparatory work
With the availability of a barrels of capacity of 50-150 liters, the barrel is fit with feeding pipe and valve, add water, ammonia, lye or desulfurization liquid, then add catalyst to the desulfurization demand for the plant with the initial dosage about 20-30PPM. After the addition of catalyst, stir the solution a few times with air blowing or wooden stick to let the catalyst dissolved in the liquid, and then wait it activation for 4 hours, during which every one hour stirring one times, to ensure full activation.
It should be noted that the liquid can not be used in the case of activated liquid in white color, and it can be used if the it is Sky-blue solution or green liquid.
(2) the input method
Feed the catalyst solution after it is fully activated, slowly and evenly to join the thin liquid sump or fluid regulator, pay attention not to add the solution to the sulfur foam layer to prevent the loss of the catalyst with the foam drainage. Three hours after activated catalyst solution into the system, a large number of bubbles of sulfur will appear, then intensive foam sulfur removal work should be done, within 1-2 days after the desulfurization the solution will return to normal.
With the deposition of sulfur and sulfur-attached cleared, the solution may be suspended/floated with high sulfur content, H2S content can sometimes fluctuate slightly after the desulphurization, then you can increase the amount of air into the same, and then the removal of the system sulfur foam is gradually turning into normal.
(3) Continued to Feeding method
Desulfurization solution composition and catalyst recruitment is calculated to device and operation conditions, then optimize the best added amount, usually it needs Cos 0.5KG for removal of 1kg H2S.
http://www.china-power-contractor.cn/Technical-Proposal-for-Desulfurization-on-300-Cubic-Meter-Biogas.html
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COMMENT: Honestly, I’m not sure about the value of this item. It would take a lot of research time, with questionable outcomes. While there are titillating possibilities, I am inclined to ignore it.
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Applied Petrochemical Research, March 2012, Volume 1, Issue 1, pp 3–19
Desulfurization of heavy oil
Rashad Javadli, ConocoPhillips , Houston
Arno de Klerk
Abstract
Strategies for heavy oil desulfurization were evaluated by reviewing desulfurization literature and critically assessing the viability of the various methods for heavy oil. The desulfurization methods including variations thereon that are discussed include hydrodesulfurization, extractive desulfurization, oxidative desulfurization, biodesulfurization and desulfurization through alkylation, chlorinolysis, and by using supercritical water. Few of these methods are viable and/or efficient for the desulfurization of heavy oil. This is mainly due to the properties of the heavy oil, such as high sulfur content, high viscosity, high boiling point, and refractory nature of the sulfur compounds. The approach with the best chance of leading to a breakthrough in desulfurization of heavy oil is autoxidation followed by thermal decomposition of the oxidized heavy oil. There is also scope for synergistically employing autoxidation in combination with biodesulfurization and hydrodesulfurization.
Introduction
Refining of crude oil to final products requires desulfurization of the oil. Fuel specifications that govern transportation fuels have over the years become increasingly stringent with respect to sulfur content. Many petrochemical products are likewise produced to be almost sulfur-free. The removal of sulfur from oil is consequently one of the central conversion requirements in most refineries and the price (and processing cost) of a crude oil is influenced by its sulfur content.
The concentration and nature of the sulfur-containing compounds change over the boiling range. The amount of sulfur in a distillation fraction increases with an increase in boiling range (Table 1) (Heinrich and Kasztelaan 2001), with the heaviest fraction containing the most sulfur. The sulfur compounds become more refractory with increasing boiling point, as the dominant compound class changes from thiols, sulfides, and thiophene in the naphtha to substituted benzothiophenic compounds in the distillate (Table 2) (Weast 1988). In the vacuum gas oil and vacuum residue, the sulfur is contained mainly in compounds of the dibenzothiophene family. The chemical nature of the sulfur has direct bearing on its removal. Desulfurization of compounds that contain aliphatic sulfur, i.e. thiols and sulfides, is easier than desulfurization of compounds that contain aromatic sulfur, i.e. thiophenics.
Keywords
Desulfurization Heavy oil Bitumen Hydrodesulfurization (HDS) Oxidative desulfurization (ODS) Biodesulfurization (BDS) Autoxidation
http://link.springer.com/article/10.1007/s13203-012-0006-6
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COMMENT: Review articles like this one can be helpful as pointers to other avenues of research. This one is interesting because one of its authors is Rashad Javadli, ConocoPhillips , Houston.
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Study on the Desulfurization of High-Sulfur Crude Oil by the Electrochemical Method
Dong Liu*†, Ming Li†, Raja L. Al-Otaibi*‡, Linhua Song§, Wen Li∥, Qingyin Li§, Hamid O. Almigrin‡, and Zifeng Yan*†
†State Key Laboratory of Heavy Oil Processing, and §College of Science, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
‡ Petrochemical Research Institute, King Abdulaziz City for Science and Technology, Post Office Box 6086, Riyadh 11442, Kingdom of Saudi Arabia
∥ Heavy Oil Development Company, Xinjiang Oilfield Company, PetroChina, Karamay, Xinjiang 834000, People’s Republic of China
Energy Fuels, 2015, 29 (11), pp 6928–6934
DOI: 10.1021/acs.energyfuels.5b01242
Publication Date (Web): September 27, 2015
Copyright © 2015 American Chemical Society
*E-mail: ldongupc@vip.sina.com., *E-mail: raletabi@kacst.edu.sa., *E-mail: zfyancat@upc.edu.cn.
Abstract
The SnSb intermetallic compound was synthesized by chemical precipitation with NaBH4 as a reducer, and then it was applied in the electrodesulfurization of Saudi crude oil as functional desulfurization material. The prepared SnSb intermetallic compound was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectrometry (EDS). Additionally, the raw material and treated oil were analyzed through gas chromatography–pulsed flame photometric detector (GC–PFPD) and gas chromatography–mass spectrometry (GC–MS). The results showed that the SnSb intermetallic compound was restored with NaBH4 with a larger particle size, lower surface area, lower crystallinity, and “brick-shaped” structure. The desulfurization efficiency for sulfocompounds with a small molecular weight is higher. It should be especially noted that benzonaphthothiophene was hardly removed by traditional hydrogenation desulfurization, whereas it could be subtracted partly via electrochemical adsorption desulfurization. The proposed desulfurization mechanism would be attributed to the adsorption reactions on the surface of the SnSb intermetallic compound.
http://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.5b01242
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COMMENT: I would read this article simply due to the fact that one of the authors is affiliated with the Petrochemical Research Institute, King Abdulaziz City for Science and Technology, Kingdom of Saudi Arabia. Oil is such a large part of the Saudi economy that any research paper produced by one of that country’s research institutes will be worth reading.
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Bioreactors for Natural-Gas Desulfurization
Authors
Brandy Raye Fidler (U. of Tulsa), Kerry Lyn Sublette (U. of Tulsa), Gary Edward Jenneman (ConocoPhillips Co), Gregory Alan Bala (Idaho Natl. Engrg. Lab)
DOI https://doi.org/10.2118/94420-STU
Document IDSPE-94420-STU
Publication Date 2005
Publisher
Society of Petroleum EngineersSourceSPE/EPA/DOE Exploration and Production Environmental Conference, 7-9 March, Galveston, Texas Publication This paper was part of a student paper session at the conference.It was included in the proceedings as STUDENT4.
Abstract
Approximately half of the reserve gas in the U.S. is subquality, meaning it contains contaminants such as hydrogen sulfide (H2S) or carbon dioxide.One of the most common problems in the gas industry is the removal and disposal of H2S also known as natural gas desulfurization or sweetening of sour gas.Many traditional methods of H2S removal are costly, energy intensive, and potentially dangerous.Therefore, these methods may not be suitable for some gas-production sites.Biological oxidation offers a safe, energy efficient, and cost-effective method for natural gas desulfurization.This laboratory has investigated biological oxidation of H2S for some time and the current research focuses on bioreactors to treat ‘stranded' natural gas.Preliminary data were previously presented at EPEC 2002[1]; this paper includes new designs and experimental data.Bioreactors utilizing the immobilization matrices Bio-Sep® and Bio-Sep®S (sufide-sorbing version) inoculated with Thiobacillus denitrificans have been used to treat a gas stream containing 10,000 ppm H2S.The desired removal efficiency is greater than 99%. Stirred-tank reactors were operated with both matrices for 3 and 8 months at maximum gas flow rates of 130 and 72 mg H2S/h for the original and sulfide-sorbing beads respectively, with removal efficiencies near 99.9%. Phospholipid fatty acid (PLFA) analysis revealed cell densities on the order of 1010 cells/g of bead.Packed-bed reactors will also be operated with both matrices.Feasibility studies will be conducted for both types of reactors. This research is ongoing with the goal of developing an economical bioreactor to treat ‘stranded' natural gas.
Background
Natural gas plays a vital role in the lives of millions of Americans.The United States is the largest consumer and the second largest producer of natural gas.Currently 85% of the gas used in the U.S. is produced in the U.S.[2] which helps decrease dependence on imported petroleum products.The demand for natural gas has increased 35% over the last decade and is expected to increase an additional 53% by 2020[2].The uses for natural gas are numerous and natural gas is also considered the cleanest fossil fuel. Pollutants such as carbon dioxide, nitrogen oxides (NOx), sulfur dioxide (SO2), particulates, and mercury are released in significantly smaller amounts when natural gas is combusted compared to oil or coal.With increasing focus on the environment and the desire to decrease our nation's dependence on imported petroleum products, natural gas is vital to the United States.
Natural gas contains impurities such as hydrogen sulfide (H2S), which must be removed before the gas is suitable for use.H2S content varies, but gas from some regions may contain as much as 50,000 ppmv H2S.Pipeline specifications are generally 4 ppmv to prevent corrosion and reduce SO2 emissions during combustion.Other problems presented by sulfides include human health risk and toxicity, reduced efficiency of fluid-handling equipment, reduced well production, reduced value of products, increased operation costs, offensive odor, and possible non-compliance with environmental regulations.Due to high capital costs, high energy usage, and increasing environmental regulations traditional desulfurization methods preclude some formations from being economically produced, leaving pockets of ‘stranded' natural gas.One method that has been investigated in this laboratory is biological oxidation of H2S. Several previous studies have shown the ability of Thiobacillus denitrificans to oxidize H2S to sulfate in one process with low energy requirements and minimal disposal products[3-9].This sulfide-oxidizing bacterium is a strict autotroph and facultative anaerobe, meaning it uses an inorganic carbon source and may grow aerobically or anaerobically.These are desirable characteristics since methane would be a potential organic carbon source and it would be dangerous to have an excess of oxygen in this system.Sulfide, elemental sulfur, and thiosulfate may be used as energy sources and each are oxidized to sulfate.Under anoxic conditions, nitrate may be used as the electron acceptor with reduction to elemental nitrogen.The reaction proceeds as follows[10]:
https://www.onepetro.org/conference-paper/SPE-94420-STU
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COMMENT: Googling® Bio-Sep results in the Bio-Sep Web site description below …
Bio-Sep Ltd was formed in 2007 to commercialise its technology and solve the problem of economically processing renewable forest, plantation and agricultural biomass into platform chemicals for the production of derived products and high value chemical intermediates.
Following 8 years of research and development, Bio-Sep has proved and patented its novel, low energy, clean fractionation technology capable of separating biomass into high purity cellulose, hemicellulose in the form of sugars, and lignin.
The Process
◾Bio-Sep uses an ultrasonic enhanced organosolv process, which permits a significant reduction in operating temperature and pressure, and therefore energy, from that required by conventional bio-refining operations.
◾The technology is simple, adaptable for a wide range of different forestry, plantation and agricultural biomass sources and greater than 90% efficient. Modular design enables small, medium and large scale standalone biorefining, or as an alternative front end for existing biorefining processes.
◾Use of non-toxic organic chemicals, ensures it is a clean process having minimal impact upon the surrounding environment.
◾The process is carbon friendly from end to end; carbon dioxide absorbed by the biomass during growth is retained throughout the refining stages.
BSL Process Diagram
.
Feedstocks
◾Lignocellulosic biomasses such as hard and soft woods, straw, miscanthus and rye grasses, sugar cane bagasse and palm waste.
◾These biomasses are cellulose, hemicellulose and lignin-rich, and upon separation there is minimal waste per tonne of feedstock.
◾Opportunity to create value by exploiting surplus feedstock and process waste, and utilise low quality unused land for the production of more biomass suitable for processing into high value chemical products.
◾Process economics realise and encourage regional social benefits for chemical production close to feedstock.
Products
◾Cellulose: platform chemicals, paper and printing products, textiles, fibres, plastics, building materials, paint, lacquers, etc.
◾Sugars: pharmaceuticals, food and drink supplements, cosmetics, domestic and personal products, veterinary and agricultural uses etc.
◾Lignin: platform chemicals, and as a binder, dispersant, emulsifier and energy source.
Pilot Plant
BIOSONIC FP7 EC Project – a successful completion of project to build and validate a prototype pilot plant is forecast for Q2 2017. Final reports have been submitted to the European Commission for review. These contain a detailed business strategy for the European Forestry Associations to exploit opportunities utilising Bio-Sep embedded technology within a bio-refinery. A blue print engineered design; software management programme; plus economic and life cycle analysis for the pilot plant have been independently concluded.
http://bio-sepltd.com/
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COMMENT: Based on the information offered by the Bio-Sep Web site, I would place this item in either 5 or 6 on the Technology Readiness scale.
In this post, we will describe a strategy for identifying technologies toward the beginning of the scale, i.e., paper concepts, bench scale developments, and, possibly, pilot scale efforts.
The strategy requires a significant amount of work to be effective. In a nutshell, it is …
Google®
Browse
Sort
In other words, enter a Google® search string, browse at least 10 pages of results, save the items you think may be useful, then scan the resulting abstracts and sort them into the appropriate Technology Readiness category.
Two useful Google® search strings you can use are …
desulfurization proposal
… and …
department of energy desulfurization
Below are the results of this search, with my COMMENT after each item indicating where I think it would fit on the Technology Readiness scale.
///////
Technical Proposal for Desulfurization on 300 Cubic Meter Biogas
Part 1: Project profiles
According to the need to design to build a set of desulfurization equipment for handling capacity of 300 m3 / h biogas desulfurization equipment.
Desulfurization design principles:
A1 use advanced, mature, reliable technology and equipment.
A2 process scheme can fully meet the requirements of national standards for civil usage of biogas.
A3 guarantee the rationality of the process and long-term stability of operation.
A4 practical and conservation investment combined.
A5. Customers actual biogas dosage of 300Nm3 / h, hydrogen sulfide content 7000PPM / Nm3, because the higher amount of hydrogen sulfide, so use processing capacity of 300Nm3 / h methane or biogas desulfurization system.
Part 2: Desulfurization equipment Process Description
1. desulfurization system process:
At present, the methane gas desulfurization process basically is divided into two types: one for dry desulfurization, and the other for wet FGD. Dry FGD is divided into iron oxide desulfurization and activated carbon desulfurization. The common problem of the two kinds of dry desulfurization methods is that the sulfur capacity of desulfurization agent is too small, less adjustment of the operation load, and difficulty of recycling of desulfurizing agent.
2. Our proposed biogas desulfurization method is Wet desulfurization method (COS method), with advantages of: stable operation performance, high desulfurizing efficiency, and lower consumption of raw materials.
With the rapid development of science and technology in recent years, we have achieved significant development in the areas of desulfurization, the desulfurizing upgrading speed quickly. The CoS new family of efficient desulfurization catalyst is developed to meet the demand of the current market demand, the newly developed high-tech innovations, technical performance has reached international advanced level. Based on extensive research of the desulfurization agent market, a detailed analysis of the advantages and disadvantages of the desulfurizer at home and abroad, collecting opinions from customers, according to the plant changes in the level of sulfur content in the actual situation and in the biogas, and constantly improve the product formulation and use of technology, developed a the CoS new highly efficient desulfurization catalyst, it has outstanding advantages of low consumption, low cost. The CoS efficient desulfurization catalyst is a kind of dual control of metal phthalocyanine cyanide cobalt compounds, a desulfurization catalyst of high activity, mainly used for liquid phase catalytic oxidation desulfurization decyanation, the desulfurization efficiency of 99% or more, decyanation efficiency of 98%, so more than 60% of the organic sulfur can be removed. And good technical, economic and social benefits have been significantly achieved for the end users. The CoS efficient desulfurization catalyst, a new generation of desulfurization catalyst produced/developed though further improvement of the active components and optimization of the production process, when compared with former catalyst, has the advantages of simplicity in production, high desulfurization efficiency, high sulfur capacity, high adoption of biogas, clear regeneration solution, less block to equipments towers, easy sulfur removal, low consumption and low cost. It is the first option as efficient desulfurization catalyst in the desulfurization of fertilizer, coking and other types of bio gas desulfurization process.
3. The physical and chemical properties of the catalyst:
Appearance: blue-gray powder.
Density: less than or equal 0.96g / cc
Main ingredients: 92%
Water insoluble matter: less than or equal 3.0% have a good solubility in water or an alkaline aqueous solution.
Soda ash in aqueous solution was sky blue, pale green in ammonia.
Does not decompose in the acid medium, good chemical stability. The catalyst itself is non-corrosive, non-toxic.
4. the usage and characteristics:
CoS desulfurization catalyst can be widely used for various types of desulfurization for gases as: biogas, producer gas, city coal gas desulfurization process gas wet air oxidation desulfurization. The product is of non-toxic, non-corrosive, non-polluting. Whether in the normal temperature and pressure or pressured conditions, regardless of ammonia or soda ash absorbent, the catalyst is able to maintain the stability of the desulfurization efficiency, when used or without additional co-catalyst. Its pre-activation process is simple, time is short, and hydrogen sulfide removal rate of up to 99%, organic sulfur removal rate of up to 60%, hydrogen cyanide removal rate of up to 98% The product has the characters of high activity, long operation life, high anti-cyanide hydrogen poisoning, it can dissolve deposition of sulfur and attached sulfur in the desulfurization unit within the system.
So it can also clean system equipment. The advantages of high sulfurization capacity, regeneration, larger suspended sulfur particles ( which is conducive to separation, do not block the tower, the removal of sulfur high purity, non-corrosive, it does not produce accumulation in the desulfurization unit without the problem of waste water treatment, no environmental pollution, can reduce the resistance of the system, reducing energy consumption, so that the equipment to extend the maintenance period, the apparent decline in the cost of desulfurization. When in operation, the process is very simple without need to change the original process, no additional equipment and very convenient to replace the old desulfurizing equipments and process.
a) On the use of devices in the liquid phase catalysis, the use of sulfur gas desulfurization:
(1), the preparatory work
With the availability of a barrels of capacity of 50-150 liters, the barrel is fit with feeding pipe and valve, add water, ammonia, lye or desulfurization liquid, then add catalyst to the desulfurization demand for the plant with the initial dosage about 20-30PPM. After the addition of catalyst, stir the solution a few times with air blowing or wooden stick to let the catalyst dissolved in the liquid, and then wait it activation for 4 hours, during which every one hour stirring one times, to ensure full activation.
It should be noted that the liquid can not be used in the case of activated liquid in white color, and it can be used if the it is Sky-blue solution or green liquid.
(2) the input method
Feed the catalyst solution after it is fully activated, slowly and evenly to join the thin liquid sump or fluid regulator, pay attention not to add the solution to the sulfur foam layer to prevent the loss of the catalyst with the foam drainage. Three hours after activated catalyst solution into the system, a large number of bubbles of sulfur will appear, then intensive foam sulfur removal work should be done, within 1-2 days after the desulfurization the solution will return to normal.
With the deposition of sulfur and sulfur-attached cleared, the solution may be suspended/floated with high sulfur content, H2S content can sometimes fluctuate slightly after the desulphurization, then you can increase the amount of air into the same, and then the removal of the system sulfur foam is gradually turning into normal.
(3) Continued to Feeding method
Desulfurization solution composition and catalyst recruitment is calculated to device and operation conditions, then optimize the best added amount, usually it needs Cos 0.5KG for removal of 1kg H2S.
http://www.china-power-contractor.cn/Technical-Proposal-for-Desulfurization-on-300-Cubic-Meter-Biogas.html
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COMMENT: Honestly, I’m not sure about the value of this item. It would take a lot of research time, with questionable outcomes. While there are titillating possibilities, I am inclined to ignore it.
///////
Applied Petrochemical Research, March 2012, Volume 1, Issue 1, pp 3–19
Desulfurization of heavy oil
Rashad Javadli, ConocoPhillips , Houston
Arno de Klerk
Abstract
Strategies for heavy oil desulfurization were evaluated by reviewing desulfurization literature and critically assessing the viability of the various methods for heavy oil. The desulfurization methods including variations thereon that are discussed include hydrodesulfurization, extractive desulfurization, oxidative desulfurization, biodesulfurization and desulfurization through alkylation, chlorinolysis, and by using supercritical water. Few of these methods are viable and/or efficient for the desulfurization of heavy oil. This is mainly due to the properties of the heavy oil, such as high sulfur content, high viscosity, high boiling point, and refractory nature of the sulfur compounds. The approach with the best chance of leading to a breakthrough in desulfurization of heavy oil is autoxidation followed by thermal decomposition of the oxidized heavy oil. There is also scope for synergistically employing autoxidation in combination with biodesulfurization and hydrodesulfurization.
Introduction
Refining of crude oil to final products requires desulfurization of the oil. Fuel specifications that govern transportation fuels have over the years become increasingly stringent with respect to sulfur content. Many petrochemical products are likewise produced to be almost sulfur-free. The removal of sulfur from oil is consequently one of the central conversion requirements in most refineries and the price (and processing cost) of a crude oil is influenced by its sulfur content.
The concentration and nature of the sulfur-containing compounds change over the boiling range. The amount of sulfur in a distillation fraction increases with an increase in boiling range (Table 1) (Heinrich and Kasztelaan 2001), with the heaviest fraction containing the most sulfur. The sulfur compounds become more refractory with increasing boiling point, as the dominant compound class changes from thiols, sulfides, and thiophene in the naphtha to substituted benzothiophenic compounds in the distillate (Table 2) (Weast 1988). In the vacuum gas oil and vacuum residue, the sulfur is contained mainly in compounds of the dibenzothiophene family. The chemical nature of the sulfur has direct bearing on its removal. Desulfurization of compounds that contain aliphatic sulfur, i.e. thiols and sulfides, is easier than desulfurization of compounds that contain aromatic sulfur, i.e. thiophenics.
Keywords
Desulfurization Heavy oil Bitumen Hydrodesulfurization (HDS) Oxidative desulfurization (ODS) Biodesulfurization (BDS) Autoxidation
http://link.springer.com/article/10.1007/s13203-012-0006-6
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COMMENT: Review articles like this one can be helpful as pointers to other avenues of research. This one is interesting because one of its authors is Rashad Javadli, ConocoPhillips , Houston.
///////
Study on the Desulfurization of High-Sulfur Crude Oil by the Electrochemical Method
Dong Liu*†, Ming Li†, Raja L. Al-Otaibi*‡, Linhua Song§, Wen Li∥, Qingyin Li§, Hamid O. Almigrin‡, and Zifeng Yan*†
†State Key Laboratory of Heavy Oil Processing, and §College of Science, China University of Petroleum, Qingdao, Shandong 266580, People’s Republic of China
‡ Petrochemical Research Institute, King Abdulaziz City for Science and Technology, Post Office Box 6086, Riyadh 11442, Kingdom of Saudi Arabia
∥ Heavy Oil Development Company, Xinjiang Oilfield Company, PetroChina, Karamay, Xinjiang 834000, People’s Republic of China
Energy Fuels, 2015, 29 (11), pp 6928–6934
DOI: 10.1021/acs.energyfuels.5b01242
Publication Date (Web): September 27, 2015
Copyright © 2015 American Chemical Society
*E-mail: ldongupc@vip.sina.com., *E-mail: raletabi@kacst.edu.sa., *E-mail: zfyancat@upc.edu.cn.
Abstract
The SnSb intermetallic compound was synthesized by chemical precipitation with NaBH4 as a reducer, and then it was applied in the electrodesulfurization of Saudi crude oil as functional desulfurization material. The prepared SnSb intermetallic compound was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectrometry (EDS). Additionally, the raw material and treated oil were analyzed through gas chromatography–pulsed flame photometric detector (GC–PFPD) and gas chromatography–mass spectrometry (GC–MS). The results showed that the SnSb intermetallic compound was restored with NaBH4 with a larger particle size, lower surface area, lower crystallinity, and “brick-shaped” structure. The desulfurization efficiency for sulfocompounds with a small molecular weight is higher. It should be especially noted that benzonaphthothiophene was hardly removed by traditional hydrogenation desulfurization, whereas it could be subtracted partly via electrochemical adsorption desulfurization. The proposed desulfurization mechanism would be attributed to the adsorption reactions on the surface of the SnSb intermetallic compound.
http://pubs.acs.org/doi/abs/10.1021/acs.energyfuels.5b01242
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COMMENT: I would read this article simply due to the fact that one of the authors is affiliated with the Petrochemical Research Institute, King Abdulaziz City for Science and Technology, Kingdom of Saudi Arabia. Oil is such a large part of the Saudi economy that any research paper produced by one of that country’s research institutes will be worth reading.
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Bioreactors for Natural-Gas Desulfurization
Authors
Brandy Raye Fidler (U. of Tulsa), Kerry Lyn Sublette (U. of Tulsa), Gary Edward Jenneman (ConocoPhillips Co), Gregory Alan Bala (Idaho Natl. Engrg. Lab)
DOI https://doi.org/10.2118/94420-STU
Document IDSPE-94420-STU
Publication Date 2005
Publisher
Society of Petroleum EngineersSourceSPE/EPA/DOE Exploration and Production Environmental Conference, 7-9 March, Galveston, Texas Publication This paper was part of a student paper session at the conference.It was included in the proceedings as STUDENT4.
Abstract
Approximately half of the reserve gas in the U.S. is subquality, meaning it contains contaminants such as hydrogen sulfide (H2S) or carbon dioxide.One of the most common problems in the gas industry is the removal and disposal of H2S also known as natural gas desulfurization or sweetening of sour gas.Many traditional methods of H2S removal are costly, energy intensive, and potentially dangerous.Therefore, these methods may not be suitable for some gas-production sites.Biological oxidation offers a safe, energy efficient, and cost-effective method for natural gas desulfurization.This laboratory has investigated biological oxidation of H2S for some time and the current research focuses on bioreactors to treat ‘stranded' natural gas.Preliminary data were previously presented at EPEC 2002[1]; this paper includes new designs and experimental data.Bioreactors utilizing the immobilization matrices Bio-Sep® and Bio-Sep®S (sufide-sorbing version) inoculated with Thiobacillus denitrificans have been used to treat a gas stream containing 10,000 ppm H2S.The desired removal efficiency is greater than 99%. Stirred-tank reactors were operated with both matrices for 3 and 8 months at maximum gas flow rates of 130 and 72 mg H2S/h for the original and sulfide-sorbing beads respectively, with removal efficiencies near 99.9%. Phospholipid fatty acid (PLFA) analysis revealed cell densities on the order of 1010 cells/g of bead.Packed-bed reactors will also be operated with both matrices.Feasibility studies will be conducted for both types of reactors. This research is ongoing with the goal of developing an economical bioreactor to treat ‘stranded' natural gas.
Background
Natural gas plays a vital role in the lives of millions of Americans.The United States is the largest consumer and the second largest producer of natural gas.Currently 85% of the gas used in the U.S. is produced in the U.S.[2] which helps decrease dependence on imported petroleum products.The demand for natural gas has increased 35% over the last decade and is expected to increase an additional 53% by 2020[2].The uses for natural gas are numerous and natural gas is also considered the cleanest fossil fuel. Pollutants such as carbon dioxide, nitrogen oxides (NOx), sulfur dioxide (SO2), particulates, and mercury are released in significantly smaller amounts when natural gas is combusted compared to oil or coal.With increasing focus on the environment and the desire to decrease our nation's dependence on imported petroleum products, natural gas is vital to the United States.
Natural gas contains impurities such as hydrogen sulfide (H2S), which must be removed before the gas is suitable for use.H2S content varies, but gas from some regions may contain as much as 50,000 ppmv H2S.Pipeline specifications are generally 4 ppmv to prevent corrosion and reduce SO2 emissions during combustion.Other problems presented by sulfides include human health risk and toxicity, reduced efficiency of fluid-handling equipment, reduced well production, reduced value of products, increased operation costs, offensive odor, and possible non-compliance with environmental regulations.Due to high capital costs, high energy usage, and increasing environmental regulations traditional desulfurization methods preclude some formations from being economically produced, leaving pockets of ‘stranded' natural gas.One method that has been investigated in this laboratory is biological oxidation of H2S. Several previous studies have shown the ability of Thiobacillus denitrificans to oxidize H2S to sulfate in one process with low energy requirements and minimal disposal products[3-9].This sulfide-oxidizing bacterium is a strict autotroph and facultative anaerobe, meaning it uses an inorganic carbon source and may grow aerobically or anaerobically.These are desirable characteristics since methane would be a potential organic carbon source and it would be dangerous to have an excess of oxygen in this system.Sulfide, elemental sulfur, and thiosulfate may be used as energy sources and each are oxidized to sulfate.Under anoxic conditions, nitrate may be used as the electron acceptor with reduction to elemental nitrogen.The reaction proceeds as follows[10]:
https://www.onepetro.org/conference-paper/SPE-94420-STU
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COMMENT: Googling® Bio-Sep results in the Bio-Sep Web site description below …
Bio-Sep Ltd was formed in 2007 to commercialise its technology and solve the problem of economically processing renewable forest, plantation and agricultural biomass into platform chemicals for the production of derived products and high value chemical intermediates.
Following 8 years of research and development, Bio-Sep has proved and patented its novel, low energy, clean fractionation technology capable of separating biomass into high purity cellulose, hemicellulose in the form of sugars, and lignin.
The Process
◾Bio-Sep uses an ultrasonic enhanced organosolv process, which permits a significant reduction in operating temperature and pressure, and therefore energy, from that required by conventional bio-refining operations.
◾The technology is simple, adaptable for a wide range of different forestry, plantation and agricultural biomass sources and greater than 90% efficient. Modular design enables small, medium and large scale standalone biorefining, or as an alternative front end for existing biorefining processes.
◾Use of non-toxic organic chemicals, ensures it is a clean process having minimal impact upon the surrounding environment.
◾The process is carbon friendly from end to end; carbon dioxide absorbed by the biomass during growth is retained throughout the refining stages.
BSL Process Diagram
.
Feedstocks
◾Lignocellulosic biomasses such as hard and soft woods, straw, miscanthus and rye grasses, sugar cane bagasse and palm waste.
◾These biomasses are cellulose, hemicellulose and lignin-rich, and upon separation there is minimal waste per tonne of feedstock.
◾Opportunity to create value by exploiting surplus feedstock and process waste, and utilise low quality unused land for the production of more biomass suitable for processing into high value chemical products.
◾Process economics realise and encourage regional social benefits for chemical production close to feedstock.
Products
◾Cellulose: platform chemicals, paper and printing products, textiles, fibres, plastics, building materials, paint, lacquers, etc.
◾Sugars: pharmaceuticals, food and drink supplements, cosmetics, domestic and personal products, veterinary and agricultural uses etc.
◾Lignin: platform chemicals, and as a binder, dispersant, emulsifier and energy source.
Pilot Plant
BIOSONIC FP7 EC Project – a successful completion of project to build and validate a prototype pilot plant is forecast for Q2 2017. Final reports have been submitted to the European Commission for review. These contain a detailed business strategy for the European Forestry Associations to exploit opportunities utilising Bio-Sep embedded technology within a bio-refinery. A blue print engineered design; software management programme; plus economic and life cycle analysis for the pilot plant have been independently concluded.
http://bio-sepltd.com/
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COMMENT: Based on the information offered by the Bio-Sep Web site, I would place this item in either 5 or 6 on the Technology Readiness scale.
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5
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system tested
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production system interface tested
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6
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Reid qualified, system installed
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production system installed and tested
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As always, this is a judgement call based on the best available information.
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The Development Of A Novel, Selective Desulfurization Process
Prof. Dr. W.H.M. Zijm,
13 september 2006
Summary
The removal of hydrogen sulfide from natural, industrial of bio gas is an operation that is frequently encountered in process industry. Driven by tight sulfur specifications and the everlasting need for cost reduction a considerable research effort is made in this field, sprouting numerous new developments in desulfurization technology. The procede desulfurization process is a regenerative process that is capable of removing H2S from a gas stream without the uptake of CO2. The removal of H2S is selective since the absorption process is based on the precipitation reaction of H2S with metal ions present in an aqueous solution under the formation of metal sulfide. The desulfurization of gas streams using aqueous iron(II)sulfate (Fe(II)SO4), zinc sulfate (ZnSO4) and copper sulfate (CuSO4) solutions as washing liquor is studied theoretically and experimentally (Chapter 2. A thermodynamic study has been used to determine a theoretical operating window, with respect to the pH of the scrubbing solution, in which the metal sulfate solution can react with hydrogen sulfide (H2S), but not with carbon dioxide (CO2) from the gas or hydroxide ions from the scrubbing solution. When the absorption is carried out in this window the proposed process should be capable of removing H2S from the gas stream without uptake of CO2 or the formation of metal hydroxides. The pH operating window increases in the order of iron, zinc to copper. Experimental verification showed that the proposed process indeed efficiently removes H2S when an aqueous Fe(II)SO4, ZnSO4 or CuSO4 solution is used as absorbent. However, for an efficient desulfurization the lower pH of the experimental pH operating window using the Fe(II)SO4 or ZnSO4 solution was higher than indicated by thermodynamics. The reason for this must probably be attributed to a reduced precipitation rate at decreasing pH. When a CuSO4 solution is used as washing liquor the solution can efficiently remove H2S over the entire pH range studied (as low as pH = 1.4). In this case only the upper pH boundary of the operating window (that indicates the possible formation of copper hydroxide or copper carbonates) seems to be a relevant limit in practice. The laboratory experiments indicate that the absorption of H2S in a CuSO4 solution, at the experimental conditions tested, is a gas phase mass transfer limited process. This allows a high degree of H2S removal in a relatively compact contactor. In addition to the lab scale experiments the potential of the new desulfurization process has also been successfully demonstrated for an industrial biogas using a pilot scale packed bed reactor operated with a fresh and regenerated CuSO4 solution. The desulfurization of gas streams using aqueous copper sulfate (CuSO4) solutions as washing liquor is subject of a more detailed investigation (Chapter 3). Absorption experiments of H2S in aqueous CuSO4 solutions were carried out in a Mechanically Agitated Gas Liquid Reactor. The experiments were conducted at a temperature of 293 K and CuSO4 concentrations between 0.01 and 0.1 M. These experiments showed that the process efficiently removes H2S. The experiments indicate that the absorption of H2S in a CuSO4 solution may typically be considered a mass transfer limited process at, for this type of industrial process, relevant conditions. The extended model developed by Al-Tarazi et al. has been used to predict the rate of H2S absorption. This model describes the absorption and accompanying precipitation process in terms of, among others, elementary reaction steps, particle nucleation and growth. The results from this extended model were compared to results obtained with a much simpler model, regarding the absorption of H2S in CuSO4 containing aqueous solutions as absorption of a gas accompanied by an instantaneous irreversible reaction. From this comparison it appeared that the absorption rate of H2S in a CuSO4 solution can, under certain conditions, be considered as a mass transfer rate controlled process. Under a much wider range of conditions the error that is made by assuming that the absorption process is a mass transfer controlled process, is still within engineering accuracy. This simplification allows for a considerable reduction of the theoretical effort needed for the design of a G/L contacting device, thereby still assuring that the desired gas specification can be met under a wide range of operating conditions. The oxidation of copper(II)sulfide to copper(II) oxide, required for the regeneration of copper sulfide is studied (Chapter 4). The possibilities for a selective and efficient method to convert copper(II)sulfide (CuS) into copper(II)oxide (CuO)of CuS are investigated. The reaction routes of the oxidation of copper sulfide as a function of reaction temperature and gas composition are established. The oxidation of copper sulfide is studied experimentally using a Thermo Gravimetric Analyzer (TGA) at temperatures ranging from 450ºC to 750 ºC and oxygen concentrations of 5 and 10 V%. It appeared that the products formed upon the oxidation of copper sulfide depend on the reaction temperature. However, in all cases the conversion time using the powdered samples was much shorter than expected based on literature results (typically 3 minutes versus 1-3 hours as mentioned in literature). The first reaction step in the oxidation of copper sulfide always was the fast decomposition of CuS into Cu2S and gaseous sulfur, which immediately is oxidized further to SO2. Subsequently, Cu2S is then oxidized, the route depending on the reaction conditions. Oxidation experiments carried out at various temperatures showed that Cu2S is oxidized selectively to CuO at temperatures above 650 ºC, while at temperatures below 650 ºC (basic) copper sulfate was also formed. The oxidation from Cu2S to CuO appeared to be the result of two consecutive reactions. Cu2S is first converted into Cu2O, which is subsequently oxidized to CuO. The experimental results allowed for the determination a rate expression and (Arrhenius) relation for the reaction rate constant of the conversion of Cu2S to Cu2O between 650 and 750 ºC and oxygen concentrations between 5 and 10 V%. The process design and economic potential of the procede desulfurization process were studied (Chapter 5). The high selectivity towards H2S of this process, along with the relatively high value of the obtained final products are key advantages. The economic performance of this process was studied using a Discounted Cash Flow analysis (DCF). The economic performance of the procede desulfurization process in comparison to its main, large scale, competitor: the amine based gas sweetening process was established. It was found that although both processes (logically) cost money when the product revenues were neglected, the economic performance of the novel process was substantially better than the economic performance of a conventional, amine based desulfurization unit. Owing to the relatively low operating costs, retrofitting an existing amine based desulfurization unit can be a very attractive option. It was also established that the competitive edge of the procede desulfurization process improved at higher CO2 or lower H2S concentrations in the feed gas, but decreases when copper losses during regeneration occur. Furthermore the economic advantage of the copper sulfate based process over the amine based process increased further when the product revenues were taken into account.
http://doc.utwente.nl/57623/1/thesis_ter_Maat.pdf
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COMMENT: Google® W.H.M. Zijm and you will find his CV, including …
Industrial Symbiosis
Industrial Symbiosis aims to aid industrial companies in sometimes quite different sectors to use residu products or waste produced by other companies as their primary input, possibly after some pre-processing. The aim is to reduce the use of fresh resources, hence to diminish the overall resource footprint. Research in this area focuses in particular on the structure and design of databases which enable companies to quickly spot potential collaborators. Furthermore, business models are designed, based on input-output theory and multi-agent systems, whereas the economics of Industrial Symbioses Networks is optimized by using game-theoretical models. As an aside, we also study the design of second generation biomass supply chains as a feeder to bio-energy. Research is based on international collaboration with both scientific and industrial countries five countries.
https://www.utwente.nl/en/bms/iebis/staff/zijm/#awards-and-services
This ties into the item highlighted above, and suggests, to me, at least, that it fits into 0 or 1 on the NASA Technology Readiness scale.
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0
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unproven concept
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basic R&D, paper concept
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1
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proven concept
/ proof of concept
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proof of concept as a paper study or
R&D experiments
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Amplification of Solar Energy Conversion and Desulfurization of Fuel at Hematite and Titania Photonic Crystals and Photonic Glass by Trapping Light
Proposal Submitted By: Lara Halaoui Professor, Department of Chemistry, American University of Beirut Email: lh07@aub.edu.lb
2013
Abstract
Significant gains in visible light absorbance and photocurrent generation were observed at frequencies to the blue of a photonic crystal stop band over a wide frequency range in quantum confined semiconductor films adsorbed on titania inverse opals. The observations raise several questions on the mechanism of light trapping in photonic crystals and disordered media, either absorbing or with absorbing matter localized therein. We propose to explore photonic effects at the blue and the red edges of the stop band on the photophysical processes and light energy conversion of absorbing matter localized in photonic crystals, and their dependence on, or tolerance to, disorder, to enhance the efficiency of third generation solar cells, solar-to-hydrogen conversion, and desulfurization of fuel. The effects of localizing a material in a nanoscale structure having a periodicity or pore size on the order of the wavelength of light will be investigated in different architectures designed as inverse opals, inverse opals with systematic variation of disorder, and photonic glass where Mie resonances are expected; and where the absorbing matter is either a quantum confined II-VI film at the interface, a molecular chromophore, or the material band itself. These findings will be applied to the design of optimum titania and hematite inverse opals or disordered inverse structures to amplify solar energy conversion in quantum dot solar cells, dye-sensitized solar cells, photoanodes for water oxidation, and the photocatalytic oxidative desulfurization of fuel by virtue of light trapping and other nanoscale effects facilitating charge separation.
https://www.aub.edu.lb/units/masri_institute/Documents/Lara%20Halaoui%20Abstracts.pdf
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COMMENT: A simple Google search string: Lara Halaoui desulfurization
Results in, among other things …
Dr. Lara Halaoui
Professor, Physical Chemistry
Postdoctoral Fellow, University of Texas at Austin, Advisor: Allen J. Bard (1998)
Ph.D. Duke University, Advisor: Louis A. Coury, Jr. (1993-1997)
B.S. with Distinction, American University of Beirut (1992)
E-mail: lh07@aub.edu.lb
Research
The central motivation of our work is to explore the unique electronic, structural, and photonic effects that emerge at the nanoscale to potentially enhance the conversion of light to electrical and chemical energy, the conversion of chemical fuel to electrical energy, and to enhance catalysis and analysis. We explore the effects of slowing light in photonic crystals and disordered media on enhancing solar energy conversion in dye sensitized solar cells and in quantum dot solar cells. We also study the photoelectrochemical behavior of quantum dot assemblies in polyelectrolytes with an interest in the effects of quantum confinement and of the nanoparticle surface on this behavior. In another theme, we are interested in electrocatalysis and sensing at the nanoscale, and study the effects of nanoparticle size, shape, and surface modification on reactivity at metal nanoparticles.
Selected Publications
◾M. El. Harakeh, L. I. Halaoui. Enhanced Conversion of Light at TiO2 Photonic Crystals to the Blue of a Stop Band and at TiO2 Random Films Sensitized with Q-CdS: Order and Disorder. J. Phys.Chem. C. 114, 2806-2813 (2010).
◾M. El Harakeh, L. Alawiyeh, S. Saouma, L. I. Halaoui. Bidirectional Photocurrent Generation at Q-CdS Assembly in Polyelectrolyte Interfaced with Hole Scavengers. Phys. Chem. Chem. Phys. 11, 5962- 5973 (2009).
◾P. Karam, L. I. Halaoui. Sensing of H2O2 at Low Surface Density Assemblies of Pt Nanoparticles in Polyelectrolyte. Anal. Chem. 80, 5441-5448 (2008).
◾Z. Estephan, L. Alawiyeh, L. I. Halaoui. Oxygen Reduction at Nanostructured Electrodes Assembled from Polyacrylate-capped Pt Nanoparticles in Polyelectrolytes. J. Phys. Chem. C 111, 8060-8068 (2007).
◾L. I. Halaoui, N. Abrams, T. E. Mallouk. Increasing the Conversion Efficiency of Dye Sensitized TiO2 Photoelectrochemical Cells by Coupling to Photonic Crystals. J. Phys. Chem. B 109, 6334-6342 (2005).
https://www.aub.edu.lb/fas/chemistry/faculty/Pages/lh07.aspx
Another result is …
Amplification in Light Energy Conversion at Q-CdTe Sensitized TiO2 Photonic Crystal, Photoelectrochemical Stability in Se2– Electrolyte, and Size-Dependent Type II Q-CdTe/CdSe Formation
Ali S. Nehme, Fatima Haydous, and Lara Halaoui*
Department of Chemistry, American University of Beirut, Beirut 110236, Lebanon
J. Phys. Chem. C, 2016, 120 (9), pp 4766–4778
Publication Date (Web): February 25, 2016
*(L.H.) E-mail: Lara.Halaoui@aub.edu.lb
This study investigates the ability of Se2– redox electrolyte to separate the photoholes and stabilize Q-CdTe quantum dot solar cell with a liquid junction. We examined the photophysical and photoelectrochemical behaviors of Q-CdTe in two sizes, green-emitting dots of 2.3–2.7 nm diameter and red-emitting dots of 4 nm diameter, in the presence of alkaline Se2– electrolyte prepared under inert atmosphere. Photoelectrochemical, absorbance, emission and emission quenching measurements revealed the presence of size dependence in Se2– surface binding to Q-CdTe, growth of type II Q-CdTe/CdSe, and stability in the photoelectrochemical cell. Emission quenching measurements show that Se2– scavenges the Q-CdTe photohole, with mechanisms that depended on size and quencher concentration. Binding of Se2– to green-emitting Q-CdTe occurred with a greater binding constant compared to the red-emitting dots, resulting in formation of type II Q-CdTe/CdSe at the smaller core indicated in red-shifted absorbance and emission spectra with incremental Se2– addition at room temperature. Photoelectrochemical measurements acquired at Q-CdTe sensitized nc-TiO2 and TiO2 inverse opal with a stop band at 600 nm, 600-i-TiO2-o, in Se2– electrolyte confirmed this redox species ability to scavenge the photohole and to protect Q-CdTe against fast photoanodic dissolution, with greater stability observed for the larger dots. Gains in the photon-to-current conversion efficiency attributed to light trapping were measured at Q-CdTe sensitized 600-i-TiO2-o relative to nc-TiO2.
http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.5b11478
COMMENT: Based on all the preceding material, I would place Professor Halaoui’s work in category 0 or 1 on the Technology Readiness scale. It shows promise, but still is largely theoretical.
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Oxidative desulphurization followed by Catalytic Adsorption Method
Article (PDF Available) · January 2014 with 705 Reads1st Syed ISHRAT Ali33.25 · University of Karachi
Abstract
The oxidative desulphurization followed by catalytic adsorption method was used for desulfurization of diesel oil. The diesel fuel was oxidized at temperature range of 70-80oC with hydrogen peroxide (H2O2) in the presence of formic acid. The effectiveness of the process mainly depends on (1) Efficient decomposition of (H2O2) in the diesel to oxidize various Organic sulfur compounds (sulfones, sulfoxides) and to extract them via polar solvent (2). Developing and analyze the catalytic adsorbent for the adsorption of unextracted aromatic sulphur compound (DBT). A porous Zeolite catalytic support mainly composed of Alumina and Silica was synthesized, and the said catalytic support loaded with Single walled carbon Nanotubes (SWNT’s) to enhance the catalyst adsorption capability.
FTIR spectral images of diesel and SEM “Scanning electron microscopic images”/EDX “Energy- dispersive X-ray” studies of catalyst provided a better qualitative approach as visual assessment of porosity and surface behavior. The proposed method can remove complex sulfur compounds from diesel fuel of high sulphur contents up to 80% in total.
Oxidative desulphurization followed by Catalytic Adsorption Method. (PDF Download Available). Available from: https://www.researchgate.net/publication/261610509_Oxidative_desulphurization_followed_by_Catalytic_Adsorption_Method [accessed Apr 13, 2017].
https://www.researchgate.net/publication/261610509_Oxidative_desulphurization_followed_by_Catalytic_Adsorption_Method
COMMENT: Rule of Thumb: Anything produced by a university research group is likely to be at the earliest stages of development. Accordingly, I would assign this item to category 0 or 1 on the Technology Readiness scale.
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Advances in Nanotechnology Transition Metal Catalysts in Oxidative Desulfurization (ODS) Processes: Nanotechnology Applied to ODS Processing
Raffaele Saladino (University of Tuscia, Italy), Giorgia Botta (University of Tuscia, Italy) and Marcello Crucianelli (University of L'Aquila, Italy)
Abstract
Organosulfur compounds show a negative environmental impact because of SOx emissions by combustion of fuel oils. As a consequence, removal of sulfur is becoming a worldwide challenge. The hydrodesulfurization (HDS) process achieves limited performances in the case of refractory S-containing aromatic compounds, such as thiophene and substituted benzothiophenes (BTs), which require highly energy-demanding conditions (high temperature and pressure conditions). Oxidative desulfurization (ODS) is considered the most promising alternative to HDS. During ODS treatment, the organosulfur compounds are oxidized to corresponding sulfoxides and sulfones, which can be successively removed by extraction with polar solvents. Different stoichiometric oxidants have been used in the ODS processes with a different degree of efficacy and environmental impact. The design and development of catalytic procedures can increase the ODS energy efficiency as well as make it more economical and environmentally acceptable. Here we describe the advances in nanostructured organometallic catalysis and biotechology applied to ODS treatment.
Chapter Preview
Top
Introduction
The removal of sulfur compounds in petroleum and fuels represents an important topic for the protection of the health of our planet, (Oliveira et al., 2013; Teixeira, Oliveira, Cristofani, & Moura, 2013). As a consequence of the combustion process, sulfur compounds are oxidized to corresponding sulfur oxides and acids that significantly influence the composition and stability of the atmospheric ozone layer, as well as the formation of acid rain, (De Souza, Guimaraes, Guerreiro, & Oliveira, 2009). These environmental risks prompted the U.S. Environmental Protection Agency (EPA) to issue a maximum sulfur content (15 ppm) in diesel fuel, a limit that was further reduced in the Euro V standard protocol (10 ppm). Thus the development of new technologies for deep sulfur removal has become an enormous challenge for production of clean fuels, (Song, 2003). The conventional procedure for the removal of sulfur contaminants in fuel is hydrodesulfurization (HDS), (Satterfeld, 1991; Speight, 1998). The HDS process consists in the hydrogenolysis reaction at elevated temperatures (ranging from 300 to 400 °C) and elevated pressures (10-130 atm) in the presence of catalysts, which are typically based on alumina or silica supports impregnated with different metal species (such as cobalt, molybdenum and nickel), (Schuit & Gates, 1973). The more challenging problems of HDS stem from the recalcitrant nature of aromatic sulfur compounds, such as benzothiophene (BT), dibenzothiophene (DBT) and other methyl substituted derivatives, which can irreversibly plug the active sites of catalyst, influencing the kinetic and the flow distribution in the reactor, (Babich & Moulijin, 2003). The oxidative desulfurization (ODS) is a promising alternative to HDS for the production of ultra low sulfur fuels, (Zannikos, Lois, & Stournas, 1995). In the ODS process, the stable and difficult-to-reduce DBT derivatives are oxidized to corresponding sulfones and sulfoxide under low temperature and pressure conditions. These polar derivatives are successively separated from the fuel by either extraction or adsorption units, (Campos-Martin, Capel-Sanchez, Perez-Presas, & Fierro, 2010). The ODS process is complementary to HDS, since some sulfur compounds, such as disulfides, are easy to be reduced but oxidize slowly. For this reason, ODS process is mainly applied for the treatment of fuel with low content of sulfur contaminants (500 ppm), already depleted of oxidation stable species, (Gatan, Barger, Gembicki, Cavanna, & Molinari, 2004). The oxidation of organic sulfur compounds is usually accomplished by the use of stoichiometric oxidants, such as potassium permanganate (KMnO4), (Gokel, Gerdes, & Dishong, 1980) sodium bromate (NaBrO3), (Shaabani, Behnam, & Rezayan, 2009) different carboxylic peracids, (Kubota & Takeuchi, 2004) sulfonic peracids (Kluege, Schulz, & Liebsch, 1996) and many other oxidants, (Shefer & Rozen, 2010; Hudlicky, 1990). On the other hand, increasing environmental concerns raised the interest to develop benign, selective and economical procedures, based on catalytic methods. Exhibiting both homogeneous and heterogeneous catalytic properties, nanocatalysts allow for rapid and selective chemical transformations, taking advantages of excellent conversion of substrate, product yield and easiness of catalyst separation and recovery (Zhang, Xu, & Wang, 2014). The high performance of these systems is related to the possibility of design nanomaterials with specific and carefully tuned catalytic properties by specific nanosized methodologies, including metal-metal oxide, metal-metal, metal-non-oxide and metal alone supporting procedures (Polshettiwar & Varma 2010). Nanosized materials show additional unique properties compared to macroscale (Campelo et al., 2009) which are associated at the high surface to volume ratio (S/V) of the catalytically active material (Teunissen, Bol, & Geus, 1999). Nanocatalysts, with dimensions of less than 100 nanometers (100 nm), have been used in ODS processes in the last years to activate primary oxidants, such as hydrogen peroxide (H2O2), alkylperoxides and peracids. In the following sections, a large panel of well recognized nanocatalysts for ODS will be described, classifying them in terms of different families on the basis of their prevalent catalytic shape like, that is nanocomposites, nanoparticles, nanotubes and more. This choice focuses on the role played by the physical form of the catalyst in synergy with the chemical properties of the metal (or metals) species in the system. Since several nanosized catalysts perform in a way similar to enzyme, a biodesulfurization (BDS) paragraph was introduced at the end to the manuscript, to better describe the scenario of environmental friendly procedures.
Source Title: Applying Nanotechnology to the Desulfurization Process in Petroleum Engineering
Copyright: © 2016 |Pages: 36
http://www.igi-global.com/chapter/advances-in-nanotechnology-transition-metal-catalysts-in-oxidative-desulfurization-ods-processes/139161
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COMMENT: Authors review the application of nanotechnology to desulfurization. As with any review article, it can provide clues for further online research. Consequently, you will want to read the article if the topic falls within your field of interest.
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Highly efficient one-pot ligation and desulfurization
Tal Moyal,a Hosahalli P. Hemantha,a Peter Siman,a Maya Refuaa and Ashraf Brik*a
Author affiliations
* Corresponding authors
a Department of Chemistry, Ben-Gurion University of the Negev, Beer Sheva, Israel
E-mail: abrik@bgu.ac.il
Fax: +972 08-647-2944
Tel: +972 08-6461195
Abstract
The combination of native chemical ligation and desulfurization is considered a powerful strategy in protein synthesis. Homogeneous desulfurization conditions based on a radical induced reaction have been widely used in the syntheses of various challenging proteins and their analogues. However, the presence of aryl thiols in the reaction mixture as a ligation catalyst hampers one-pot ligation/desulfurization, hence mandating additional purification/lyophilization steps prior to desulfurization. This significantly reduces the yield and prolongs the ligation process. Here we report that the use of preformed peptide-aryl thioester allows for efficient one-pot ligation and desulfurization. This approach was tested successfully for various model peptides including the synthesis of ubiquitin from two fragments. However, in the case of the synthesis of di-ubiquitin chains, where the ligation is mediated by δ-mercaptolysine to form an isopeptide bond, excess aryl thiol was required for efficient ligation, necessitating purification prior to desulfurization. To overcome these obstacles, we found that functionalization of the aryl thiol with a hydrazide moiety enabled, after the ligation step, its capture by resin-aldehyde to permit direct desulfurization. Altogether, these approaches should facilitate protein synthesis with improved efficiency in yields and time.
http://pubs.rsc.org/-/content/articlelanding/2013/sc/c3sc50239b#!divAbstract
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COMMENT: This falls into the category of pure research. Accordingly, I place it in category 0 or 1 on the Technology Readiness scale.
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Information Systems Division, National Agricultural Library
The National Agricultural Library is one of four national libraries of the United States, with locations in Beltsville, Maryland and Washington, D.C. It houses one of the world's largest and most accessible agr [...]
HOMEPAGE: http://www.nal.usda.gov/
Effect of transition metal oxides catalysts on oxidative desulfurization of model diesel [2012]
Bakar, Wan Azelee Wan Abu Ali, Rusmidah Kadir, Abdul Aziz Abdul Mokhtar, Wan Nur Aini Wan
Abstract
In this paper, model diesel is used to study the performance of oxidative desulfurization (ODS) system compared to hydrodesulfurization (HDS) process. A detailed parametric experimental study was performed to select the best technique for sulfur removal. The effects of solvent, oxidant, bimetallic oxide catalyst, dopant, dopant ratio and calcination temperature were investigated. Dimethylformamide (DMF) and tert-butyl hydroperoxide (TBHP) were found to be the best solvent and oxidizing agent for the removal of sulfur compounds in model diesel. Both solvent and oxidant were then applied to explore the applicability of various catalysts, such as iron, manganese, molybdenum, tin, zinc and cobalt in model diesel. The results showed that the catalytic activity was decreased in the order: Mo>Mn>Sn>Fe≈Co>Zn. Further investigation of doped molybdenum revealed that 4.35% WO₃/16.52% MoO₃/Al₂O₃ in the ratio of 10:90 with calcination temperature at 500°C was assigned as the best catalyst in this research. Under mild reaction condition, this catalyst showed high conversion with appreciable stability until 150hours and can be used as a reusable active catalyst in ODS treatment. Additionally, on the basis results obtained, a mechanistic proposal for this reaction was postulated, as an oxidation mechanism by nucleophilic attack of the sulfur atom on peroxo species of WO₃/MoO₃/Al₂O₃.
http://agris.fao.org/agris-search/search.do?recordID=US201600066642
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COMMENT: Again, this appears to fall into category 0 or 1 on the Technology Readiness scale.
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Researchers at Advanced Energy Materials, LLC Win TiEcon’s Top 50 Startup Award
Company Closes On an SBIR Phase II grant from the National Science Foundation for $750,000
Louisville-based Advanced Energy Materials, LLC (AdEM) has been selected as a Winner of the Top 50 Startups in 2014 by the prestigious TiECon Awards Program in Santa Clara, CA. In addition, the company successfully was awarded its first SBIR Phase II grant this summer from the National Science Foundation for a total award of $750,000.
AdEM is a spinoff company of the University of Louisville, researching fuel improvements, fuel alternatives, and nanowire applications to improve energy efficiencies. The company holds an exclusive license agreement, with a patent portfolio of 9 issued and 4 pending U.S. patents through the University of Louisville Research Foundation’s Office of Technology Transfer. The original technology was developed by researchers at University Louisville’s Conn Center for Renewable Energy Research. The innovations include processes for making advanced nanomaterials and their formulations for catalysts, adsorbents, composites and batteries.
TiEcon’s 50 is the TiE Silicon Valley’s premier annual awards program, drawing competition from thousands of technology start-ups worldwide. Awards are announced at TiEcon, the world’s largest conference for entrepreneurs annually. TiE is a global, not-for-profit network of entrepreneurs and professionals dedicated to the advancement of entrepreneurship. The TiE50 track record since inception in May 2009 shows that 94% of the winners and finalists have been funded. Click here for TiE50 Winners - 2014.
TiECon’s Top50 Award Winner interview for Advanced Energy Materials.
AdEM has been awarded its first SBIR Phase II grant through the National Science Foundation for its proposal titled “Advanced Hydrodesulfurization Catalysts”. During the Phase I, AdEM developed a high performance catalyst product, “AdeSulfur™”. This advanced catalyst accomplishes desulfurization for lowering sulfur levels well below the levels possible with currently available catalyst technologies.
The high performance catalyst technology has the potential beyond sulfur removal for a number of other technological applications such as sulfur tolerant hydrogenation within chemical industry. Using the funds in Phase II, the company intends to demonstrate commercial scale production at tons per day.
“Sulfur removal has become significant for transportation fuels due to increased environmental regulations. Any sulfur content in the fuel makes it poisonous for specific applications such fuel cells. As such, a sulfur removal catalyst that does not leave any trace of sulfur has a huge impact to the market,” explained Vasanthi Sunkara, CEO of AdEM.
Dr. Neville G. Pinto, Dean of the University of Louisville J. B. Speed School of Engineering, explained further. “The success of this start-up is an excellent example of how basic research at the University of Louisville Conn Center for Renewable Energy can translate into a technological solution to an important societal need, in this case the development of an alternative fuel. The company is on a robust path for success with the potential to impact job creation significantly in the longer term,” he said.
About AdEM:
Advanced Energy Materials, LLC (AdEM) is an early stage company that conducts research and development of catalytic technologies for ultra-deep desulfurization and aromatic saturation in fuels. The company was founded in 2009 to commercialize patented technology from the University of Louisville. AdEM’s unique competency in the bulk manufacturing of nanowires affords a significant advantage in the discovery, development, and patenting of nanowire-based materials for energy applications and will maintain our advantage in scalable nanowire manufacturing.
Due to their unique properties, nanostructured materials are being increasingly utilized in emerging renewable energy applications such as desulfurization catalysts, anode materials for lithium-ion batteries, solar cells, capacitors, and composites. AdEM’s catalyst product “AdeSulfur™” is nickel-supported on zinc-oxide Nanowire, and alumina based powder for deep desulfurization of a variety of fuels including diesel, gasoline, kerosene and jet fuels.
Prior funding for AdEM includes, two SBIR Phase I grants through the National Science Foundation and two SBIR matching grants through the Kentucky Cabinet for Economic Development’s SBIR match program. Kentucky’s SBIR program matches all or part of federal SBIR awards received by Kentucky-based companies. AdEM’s laboratory is currently located in the Nucleus Innovation Park TechCenter at 201 E. Jefferson St. in downtown Louisville. For more information on AdEM’s products and capabilities, please visit advancedenergymat.com
http://www.advancedenergymat.com/AdEM-wins-TiEcons-Top-50-Startup-Award.html
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COMMENT: This appears to describe a technology transfer effort that is on the verge of becoming commercially viable. As such, it appears to fit into category 2, 3, or 4 on the Technology Readiness scale.
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2
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validated concept
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experimental proof of concept using
physical model tests
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3
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prototype, prototype tested
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system function, performance and
reliability tested
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4
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environment tested
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preproduction system environment tested
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Operational aspects of the desulfurization process of energy gases mimics in biotrickling filters.
Fortuny M1, Gamisans X, Deshusses MA, Lafuente J, Casas C, Gabriel D.
Author information
1Department of Chemical Engineering, Universitat Autònoma de Barcelona, Bellaterra, Spain.
Abstract
Biological removal of reduced sulfur compounds in energy-rich gases is an increasingly adopted alternative to conventional physicochemical processes, because of economical and environmental benefits. A lab-scale biotrickling filter reactor for the treatment of high-H(2)S-loaded gases was developed and previously proven to effectively treat H(2)S concentrations up to 12,000 ppm(v) at gas contact times between 167 and 180 s. In the present work, a detailed study on selected operational aspects affecting this system was carried out with the objective to optimize performance. The start-up phase was studied at an inlet H(2)S concentration of 1000 ppm(v) (loading of 28 g H(2)S m(-3) h(-1)) and inoculation with sludge from a municipal wastewater treatment plant. After reactor startup, the inlet H(2)S concentration was doubled and the influence of different key process parameters was tested. Results showed that there was a significant reduction of the removal efficiency at gas contact times below 120 s. Also, mass transfer was found to be the main factor limiting H(2)S elimination, whereas performance was not influenced by the bacterial colonization of the packed column after the initial startup. The effect of gas supply shutdowns for up to 5 days was shown to be irrelevant on process performance if the trickling liquid recirculation was kept on. Also, the trickling liquid velocity was investigated and found to influence sulfate production through a better use of the supplied dissolved oxygen. Finally, short-term pH changes revealed that the system was quite insensitive to a pH drop, but was markedly affected by a pH increase, affecting both the biological activity and the removal of H(2)S. Altogether, the results presented and discussed herein provide new insight and operational data on H(2)S removal from energy gases in biotrickling filters.
https://www.ncbi.nlm.nih.gov/pubmed/21890165
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COMMENT: Based on the description of a lab-scale biotrickling filter reactor, this item may fit into one of the following categories …
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2
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validated concept
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experimental proof of concept using
physical model tests
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3
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prototype, prototype tested
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system function, performance and
reliability tested
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Comparison of a New Warm-Gas Desulfurization Process versus Traditional Scrubbers for a Commercial IGCC Power Plant
Jerry Schlather, Eastman Chemical Company
Brian Turk, RTI International
Gasification Technologies Conference, October 17, 2007
Technology Readiness for Commercial Deployment
•Performance in real syngas
–Field testing has provided actual performance resulting from exposure to real coal-derived syngas
•Process reliability
–Sorbent performance
•Extended testing to evaluate long-term chemical deactivation and mechanical attrition
–Process control and stability
•Demonstrated and refined ability to control process at stable operating conditions
•Sorbent production scale-up
–Commercially manufactured 8,000 lbs of sorbent for pilot-plant testing
•Process scale-up
–Successfully scaled process up to 0.3 MW
–Actively working on a 50-MW demonstration unit
•Modular fixed bed cleanup technologies for additional syngas contaminants
–Fixed bed adsorbents for HCl, NH3, As, Hg, and Se
www.gasification-syngas.org/uploads/eventLibrary/55SCHL.pdf
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COMMENT: This item looks like it fits into one or both of the following two categories …
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6
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Reid qualified, system installed
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production system installed and tested
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7
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field proven
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production system field proven
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Ind. Eng. Chem. Res. 2010, 49, 5561–5568
Oxidative Desulfurization of Jet and Diesel Fuels Using Hydroperoxide Generated in Situ by Catalytic Air Oxidation
Ramanathan Sundararaman, Xiaoliang Ma, and Chunshan Song*
Clean Fuels and Catalysis Program, EMS Energy Institute and Department of Energy and Mineral Engineering, The Pennsylvania State University
To whom correspondence should be addressed. Tel.: 814 863 4466.
E-mail: csong@psu.edu.
The objective of this work is to explore the potential of carrying out oxidative desulfurization using air as an oxidant. The liquid fuels to be desulfurized were first contacted with air to produce hydroperoxides in situ, which were then used as selective oxidants to oxidize the sulfur compounds. Unsupported CuO was tested as a catalyst for producing hydroperoxides in the fuel at 120 °C in the presence of air. Air oxidation was also carried out in the presence of Al2O3-supported CuO and also noncatalytically. Unsupported CuO was substantially more active than the other two cases. The yield of the hydroperoxides depends strongly on the catalyst and the reaction temperature; the yield decreased in the order of 120 °C > 140 °C.100 °C but the rate of oxidation to produce hydroperoxides decreased in the order of 140 °C > 120 °C . 100 °C. It was found that more hydroperoxides could be generated in diesel fuel than in jet fuel, which might be related to the higher concentration of alkyl aromatics in diesel fuel when compared to JP-8 jet fuel. The hydroperoxides generated in situ were then used to oxidize the sulfur compounds in the fuel in the presence of SiO2-supported MoO3 catalyst. Hydroperoxides generated in situ were effective in oxidizing the alkyl-substituted benzothiophene and dibenzothiophene present in jet and diesel fuels to their corresponding sulfones which were then removed by adsorption on beta zeolite. On the other hand, the amount of cumene hydroperoxide required per mole of S for oxidation to sulfone was 1.5 and 10 times higher than the stoichiometric amounts for JP-8 jet fuel and diesel fuel, respectively. This study demonstrates that oxidative desulfurization can be effectively carried out by using air as an oxidant for generating hydroperoxides in situ, which can then be used to selectively oxidize the sulfur compounds to sulfones, thereby eliminating the need for use, storage, and handling of expensive liquid-phase peroxide oxidants.
1. Introduction
“U.S. EPA Tier 2” emissions specifications and “EU Euro IV” standards called for sulfur in diesel fuel to be reduced to a maximum of 15 and 10 ppmw S, respectively, and many countries around the world are pursuing toward ultralow sulfur diesel (ULSD) fuels.1-4 These strict sulfur mandates led to a surge of development of alternative desulfurization technologies because of the increased difficulty in removing the last few alkyl substituted dibenzothiophenes, especially 4,6-dimethyl dibenzothiophene (4,6 DMDBT) from diesel fuels.3,5 Given the long lead times involved for developing alternative technologies, most refiners made investment plans for meeting these tight specifications by employing conventional hydrodesulfurization (HDS), which is a simple and proven process for the refiners. This has led to HDS units operating at increased severity and/or with higher catalyst volumes contributing to higher operating costs but with diminishing returns for ultralow sulfur fuels.1,6 Among the alternative technologies proposed in the literature, oxidative desulfurization (ODS) has gained attention because of its mild operating conditions coupled with no hydrogen requirement for ULSD. More importantly, the substituted dibenzothiophenes such as 4,6-DMDBT, which is the least reactive for HDS, could show increased oxidation activity under certain conditions. So implementation of ODS as a finishing step to ULSD that complements HDS has also been discussed in the literature.7 Most of the ODS approaches reported in the literature involve selective oxidation of sulfur compounds to corresponding sulfones by liquid oxidants followed by adsorption or extraction to remove them for ULSD. The use of liquid oxidants has plagued ODS technology because of the increased cost in handling and storage of the liquid oxidants. Some examples of liquid oxidants used in prior studies include hydrogen peroxides, tert-butyl hydroperoxide, tert-butyl hypochlorite, and nitric acid, etc.8-15 To overcome the issue of usage of these expensive oxidants, the use of oxygen and ozone has been proposed in the literature but the issue of selectivity to sulfur compounds was not addressed clearly.16,17 Use of oxygen as an oxidant with sacrificial aldehyde has also been proposed in the literature for selective oxidation of sulfur compounds,18 and a novel process based on catalyst free, solvent assisted oxidative desulfurization of fossil fuels by air was reported recently.19 However, the use of expensive oxidants, oil-insoluble oxidants which result in biphasic reaction and the use of sacrificial agents, has rendered ODS as an unfavorable technology. In this study, ODS was carried out by a two-step in situ air oxidation procedure coupled with adsorption, and the scheme of the process is shown in Figure 1. In the first step, the fuel is mixed with air in the presence of a catalyst to produce hydroperoxides in situ. The hydroperoxide generated in the fuel then oxidizes the sulfur compounds present to their corresponding sulfones in the second step in the presence of a catalyst. The generated sulfones were then removed by adsorption for ultralow sulfur fuels. In regard to this, a commercial JP-8 jet fuel with 520 ppmw S and a commercial diesel fuel with 41 ppmw S were tested for ODS by the process scheme as described in Figure 1. JP-8 jet fuel was also employed here because of the renewed interest in using jet fuel feedstock as a precursor for fuel cell applications, which calls for very low levels of sulfur as the sulfur compounds are detrimental to the fuel processor and to the fuel cell itself.20,21
www.canli.dicp.ac.cn/Gruop%20Seminars%20Pdf/20100828ynzhang.pdf
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COMMENT: Reported by the highly regarded Chun Song research group, this item probably fits into the following category …
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1
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proven concept
/ proof of concept
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proof of concept as a paper study or
R&D experiments
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Argonne National Laboratory
Hydrogen from Steam-Methane Reforming with CO2 Capture
John C. Molburg (molburg@anl.gov ; 630-252-3264)
Richard D. Doctor (rdoctor@anl.gov ; 630-252-5913)
20th Annual International Pittsburgh Coal Conference, September 15-19, 2003, Pittsburgh, PA
ABSTRACT
The U.S. Department of Energy (DOE) is investigating employing CO2-capture technologies combined with Texaco and Shell integrated gasification combined-cycle (IGCC) power systems that produce both merchant hydrogen and electricity. This represents a high efficiency strategy for using the coal-resource base while being sensitive to the current motivation to reduce greenhouse gas emissions. An oxygen-blown entrained gasifier served as the basis for the study. Comparisons of energy penalties, capital investment, and CO2 emission reductions were based on the full-energy cycle including mining, coal transportation, coal preparation, gasification, gas treatment, power generation, infrastructure to transfer power or hydrogen to end users, and pipeline transport of CO2 to sequestration. Technical aspects of H2 pipelines and supercritical CO2 pipelines, as well as issues relating to CO2 sequestering in a variety of host reservoirs were considered. Results from process design and economic simulation of a Benchmark Steam-Methane- Reforming (SMR) system make it possible to test at what price the cost of methane makes coal-base hydrogen economical. An ASPEN model of SMR with heat integration is the basis for a review of performance issues related to natural gas feed composition, desulfurization pretreatment, reforming, gas conversion and purification. Sensitivity studies have been performed to examine the effects of changes in operating pressure, steam-to-carbon ratio, and the use of combustion air preheat. Other parameters that affect hydrogen production and fuel use are reformer reactor inlet and outlet temperatures, shift strategy, reactor temperatures, and PSA design and operation.
Overview
The steam-methane reforming (SMR) process is illustrated in Figure 1. The basic steps leading from the hydrocarbon feed, which we assume to be natural gas, to the high purity hydrogen product are: pretreatment of the raw feed, reforming to synthesis gas, conversion to a hydrogen-rich gas, and purification to hydrogen product specifications. This basic SMR process is supported by a process furnace, which provides heat to raise the gas temperature for the endothermic pretreatment and reforming processes. The furnace also provides heat to raise steam, which is used as a reagent in both reforming and gas conversion. Note that gas conversion, which is exothermic, also provides heat for raising steam. The furnace consumes natural gas as fuel and process gas, which is a residual from the hydrogen purification process. While it provides a highly simplified representation of the process, Figure 1 still illustrates the high level of heat and materials integration used in an SMR plant. Heat exchangers in the furnace flue gas stream heat the feed for pretreatment, pre-reforming, and reforming. The heat recovery steam generator extracts heat for feedwater heating, evaporation, and superheating from the furnace exhaust and from gas conditioning. Steam used as a reagent is partially recovered by condensation from the converted gas stream. A closed water system would clean this water stream and reuse it as boiler feedwater. Steam is also used as a heat source for the MDEA process, which removes CO2 as a part of the purification process. Purification results in some waste, but also in the recycle process fuel stream. A trade-off in SMR plant design and operation is the distribution of natural gas consumption between feed and fuel. Optimization of plant operating parameters for high hydrogen production results in low process gas production and, consequently, greater fuel use. Full representation of all these heat and materials interactions results in a model with multiple nested material and energy loops. Such multiple loops can be represented in ASPEN, but result in a model which is difficult to converge as parameters are varied to study the implications of process design choices. To provide a robust model for sensitivity studies, we have created a simplified model by removing most of the heat exchangers and steam production from the full model. The thermodynamic integrity of the simplified model is assured by setting appropriate reactor temperatures and flow stream temperatures exogenously. Most of the model description below is based on this simplified model, which is represented in Figure 2.
http://www.google.com/url?sa=t&rct=j&q=&esrc=s&source=web&cd=1&cad=rja&uact=8&ved=0ahUKEwjciOPMy6TTAhUMySYKHVBZDF8QFgglMAA&url=http%3A%2F%2Fwww.uxc.com%2Fsmr%2FLibrary%255CAlternative%2520Uses%2F2003%2520-%2520Hydrogen%2520from%2520Steam-Methane%2520Reforming%2520with%2520CO2%2520Capture.pdf&usg=AFQjCNFaAgLvb6vQ2e1Xzi5XaYDmQNZgog&bvm=bv.152479541,d.eWE
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COMMENT: At benchmark scale, I would place this in category 2, but it could fit in category 3.
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2
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validated concept
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experimental proof of concept using
physical model tests
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3
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prototype, prototype tested
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system function, performance and
reliability tested
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Use of a Circulating Fluid Bed for Flue Gas Desulfurization
John G. Toher, Lurgi-Lentjes N. America
2002
Abstract
U.S. utilities are faced with new economic challenges to remain competitive in light of deregulation initiatives. In addition, regulatory requirements are forcing many of these utilities to reduce sulfur dioxide emissions and be prepared to reduce additional pollutants such as mercury vapor and fine particulate from coal-burning plants. Technology choices for regulatory compliance are either wet or dry flue gas desulfurization (FGD) systems. Wet scrubbers are more capital intensive but are the technology of choice for large power plants where single vessel capacity and operating costs can be more favorable. The lower cost dry FGD system is likely to play a greater role in compliance strategies for Phase II of the revised CAAA of 1990. The technology described here has been in commercial use in the European power industry since 1987 and more recently since 1995 in the N. American power industry. The Lurgi Lentjes N. America dry FGD technology employs a circulating fluid bed (CFB) of fly ash and scrubber by-product to achieve a high particle density. Hydrated lime injected into the circulating bed adsorbs sulfur dioxide and trioxide with very reasonable utilization of the lime, due to its high residence time in the recirculating bed. Fine particles entering the system are formed into larger agglomerates through collision with the bed particles. A conventional electrostatic precipitator or fabric filter can then readily capture the larger particles leaving the bed. An additional advantage is the multi-pollutant control capability of this technology. It is of great interest to the regulatory authorities as well as the utility industry. The U.S. department of energy (DOE) has selected this technology from twenty-four proposals, to demonstrate cost effective simultaneous control of mercury, acid gases (HF, HCl, SO3), fine particulate, and other HAPs in a single vessel. This demonstration is scheduled for completion, at the 100-megawatt size, in the next couple of years. Introduction Lurgi Lentjes N. A. is part of the global technology company mg engineering, a leading international supplier of technological solutions to the power, chemical, and metallurgical industries. As an operating company under Lurgi Lentjes AG, they provide N. America a link to the innovative solutions of a $1.0 B (US) worldwide power plant and gas cleaning technology company. Their gaseous environmental solutions consist of high and low dust denitrification, wet and dry flue gas desulfurization utilizing limestone, ammonia, seawater, quick and hydrated lime. The particulate control solutions consist of fabric filters and electrostatic precipitators. Since 1910, they have provided global EPC services and have secured 20% of the total worldwide air pollution control market. The Bush administration is emphasizing use of existing coal-fired plants as a short-term means of mitigating power supply problems. Simultaneously, there is need to further reduce emissions of SO2 from these plants. Actual emissions for 2001 exceeded allocations for the same year by approximately 1.4 million tons.1 If no further reductions occur, actual emissions will exceed allocations by more than 1.9 million tons annually as allocations are further reduced by half a million tons in 2010. Initially the bank of saved allowances from phase I will be used to offset actual emissions that are expected to remain above the national goal. As these saved or "banked" allowances are depleted, the allowed and actual emissions are expected to converge. Industry and regulatory experts predict the crossover point to be the year 2010. To support this FGD market, Lurgi terminated its previous licensing agreement in the U.S. and opened the LLNA offices in Columbia, Maryland. The average unit size in the phase II market is smaller than phase I and this favors the "circulating" type of dry scrubber technology from LLNA. This paper presents a history of the circulating scrubber technology and a cost comparison from the owner's perspective.
http://www.carmeusena.com/sites/default/files/brochures/flue-gas-treatment/tp-cfb-20fgd-2.pdf
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COMMENT: This item is dated 2002. Much can happen in 15 years, so further online research would be required to determine where this demonstration project went, and whether it became commercially viable.
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J. Phys.: Condens. Matter 25 (2013) 252201 (5pp) doi:10.1088/0953-8984/25/25/252201
Fast Track Communication
Controlled argon beam-induced desulfurization of monolayer molybdenum disulfide
Quan Ma1, Patrick M Odenthal1, John Mann1, Duy Le2, Chen S Wang1, Yeming Zhu1, Tianyang Chen1, Dezheng Sun1,3, Koichi Yamaguchi1, Tai Tran1, Michelle Wurch1, Jessica L McKinley1, JonathanWyrick1, KatieMarie Magnone1, Tony F Heinz3, Talat S Rahman2, Roland Kawakami1 and Ludwig Bartels1
1 Chemistry, Physics, and Materials Science and Engineering, University of California, Riverside, CA 92521, USA
2 Department of Physics, University of Central Florida, Orlando, FL 32816, USA
3 Departments of Physics and Electrical Engineering, Columbia University, New York, NY 10027, USA
E-mail: Ludwig.Bartels@ucr.edu
Published 24 May 2013
Abstract
Sputtering of MoS2 films of single-layer thickness by low-energy argon ions selectively reduces the sulfur content of the material without significant depletion of molybdenum. X-ray photoelectron spectroscopy shows little modification of the Mo 3d states during this process, suggesting the absence of significant reorganization or damage to the overall structure of the MoS2 film. Accompanying ab initio molecular dynamics simulations find clusters of sulfur vacancies in the top plane of single-layer MoS2 to be structurally stable. Measurements of the photoluminescence at temperatures between 175 and 300 K show quenching of almost 80% for an 10% decrease in sulfur content.
attention as one of the interesting atomically thin materials beyond graphene [1–3]. Like graphene, it can be prepared in a stable form down to monolayer thickness. In contrast to graphene, however, MoS2 has an intrinsic band gap: the indirect bandgap of bulk MoS2 of 1.4 eV crosses over to a direct optical bandgap of 1.9 eV in the monolayer limit [4, 5]. In addition to this interesting electronic structure, MoS2 has many established applications in catalysis, such as for hydrodesulfurization [6, 7], and it recently received attention as an electrode material for water splitting [8, 9]. Single-layer MoS2 field effect transistors have been fabricated with mobilities on the order of 1 cm2 V1 s1 and higher [10–13], as well as on–off ratios up to 108 at room temperature. Bulk MoS2, and most mono- or few-layer MoS2 materials examined to date, exhibit n-doping [10–15], but p-doping has also been observed [16]. Ambipolar operation has been achieved by gating with an ionic liquid [17]. Another distinctive electronic property is the possibility of selective valley population of the monolayer, which has been achieved using excitation by circularly polarized light [18–22]. Although many of the studies to date have made use of mechanically exfoliated single-layer MoS2 films [23], MoS2 monolayers can also be prepared by means of chemical vapor deposition (CVD). A variety of substrates, including Cu [24], Au [16, 25–27], SiO2 [16, 28], and various other insula- tors [13, 16, 29], have been successfully used for growth. Molybdenum–sulfur compounds with stoichiometry different from MoS2 have been reported in CVD deposition, including Mo6S6 nanowires [30, 31] and Mo2S3 films [32, 33]. Like graphene, single-layer MoS2 is stable in air for extended periods of time. In carbon-based materials, such as nanotubes and graphene, this high stability, while attractive for many purposes, has proven a challenge for other needs. Intense processing is required, for example, to bond covalently to these materials, to render them soluble, and to alter their electronic properties, such as by hydrogenation or partial oxidation of graphene. For MoS2, the inertness of the basal plane calls for interventions to facilitate chemical reactions. In this regard, theoretical studies indicate that sulfur vacancies are reactive [34, 35].
In this paper we show that sputtering with low-energy ArC ions can transform single-layer MoS2 all the way to MoS1:5, while in situ x-ray photoelectron spectroscopy (XPS) reveals substantially unchanged Mo 3d states. In situ monitoring of the photoluminescence (PL) allows us to gauge the impact of the sputter-induced defects/vacancies on the exciton dynamics; in the temperature regime between 175 and 300 K we find a decay of PL yield that decreases at 7.0 0.5 times the rate of sulfur removal. Our measurements were performed on films and isolated islands of single-layer MoS2 grown on a SiO2 substrate from MoO3 and elemental sulfur, as described elsewhere [36]. Figure 1(a) shows an optical microscopy image of a representative area of a MoS2 film used in this study. Figure 1(b) is a schematic representation of the structure of single-layer MoS2, which consists of hexagonal top and bottom layers of sulfur surrounding a molybdenum layer. The samples were characterized in air prior to our experiments using Raman and PL spectroscopy. The right portion of the image in figure 1(a) shows a continuous film of monolayer thickness, while the left area consists of single-layer MoS2 islands. Both regions exhibit the same PL peak at 1.87 eV, corresponding to the direct band gap. Raman spectra reveal the E1 2g and A1g modes, with a separation of 21 cm1, as is typically seen in single-layer MoS2 films prepared by CVD [16, 37]. Once a sufficiently homogeneous area of the MoS2 film exhibiting exclusively single-layer Raman and PL characteristics had been identified, the sample was attached to a temperature-controlled manipulator in an ultra-high vacuum system. For subsequent studies of sputtering, the system was evacuated and baked to reach a base pressure of 1[1]109 Torr. A Varian sputter gun operated at 500 V acceleration potential, 20 mA emission current, and 5 [1] 106–2 [1] 105 Torr partial pressure of Ar was used for generating ArC ions. The sputter beam had a diameter of 0.5 cm. For reference, we measured the sputter current induced by this beam on a copper surface as 0:6–2:2 A, respectively, for the Ar pressures given above. In the following, we will assume this value as an approximation of the beam current. The XPS measurements were performed using excitation by Al K
radiation with the emitted electrons detected by a Scienta R300 hemispheric analyzer equipped with a 2D detector. The PL experiments employed a Spectra Physics Millennia laser operating at a wavelength of 532 nm, a spectrometer with 1200 lines mm1 grating blazed at 750 nm, and a liquid-nitrogen cooled Princeton Instruments SPEC-10 CCD detector. For in situ measurements a 50 mm focal length lens inside our UHV system was used to focus 100 mW of pump beam onto the sample surface with a spot of 100 m. This results in an intensity of approximately 10 W m2, similar to that of typical microscope-based Raman measurements [4]. We collected the resultant PL signal in the back-scattered direction using a dichroic mirror to separate the excitation beam from PL signal. Vacancy formation energy and thermal stability of the sputtered film was evaluated using the Vienna ab initio simulation package (VASP) [38, 39] to perform density functional theory (DFT) simulations.We employed projectoraugmented wave (PAW) [40, 41] and plane-wave basis set methods. We used the Perdew–Burke–Ernzerhof of functional (PBE) [42] to describe exchange correlation interactions and adopted a cut-off for plane-wave expansion at 500 eV. The conjugate-gradient algorithm [43] was employed
http://iopscience.iop.org/article/10.1088/0953-8984/25/25/252201/meta
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COMMENT: I would place this item in category 1 on the Technology Readiness scale …
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1
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proven concept
/ proof of concept
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proof of concept as a paper study or R&D experiments
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DOE/NETL-2001/1141
LIFAC Sorbent Injection Desulfurization Demonstration Project: A DOE Assessment
January 2001
U.S. Department of Energy
National Energy Technology Laboratory
Morgantown, WV 26507-0880
and
P.O. Box 10940, 626 Cochrans Mill Road
Pittsburgh, PA 15236-0940
website: www.netl.doe.gov
Executive Summary
This document serves as the U.S. Department of Energy (DOE) post-project assessment of the Clean Coal Technology (CCT) Round III project LIFAC Sorbent Injection Desulfurization Demonstration Project. In 1990, LIFAC North America, Inc. entered into cooperative agreement no. DE-FC22-90PC90548 with Richmond Power and Light Company (RP&L), which provided the host site and served as a cofunder. DOE provided 50 percent of the total project cost of $21 million. Other cofunders were ICF Kaiser Engineers, Tampella Power Corporation, Electric Power Research Institute (EPRI), Black Beauty Coal Company, and the State of Indiana. The demonstration was conducted in Richmond, Wayne County, Indiana, at RP&L’s Whitewater Valley Station Unit 2 (a 60-MWe boiler) between September 1992 and June 1994. The abbreviation LIFAC refers to the process, which involves limestone injected into the furnace with activation of untreated calcium oxide. LIFAC technology is designed to remove sulfur dioxide (SO2) produced in a coal-fired utility boiler, using a limestone sorbent at a calcium/sulfur molar ratio of 2.0-2.5/1. A unique feature of this technology is humidification of the flue gas in a separate activation reactor, which increases SO2 removal. An electrostatic precipitator downstream from the point of injection captures the reaction products, along with the fly ash entrained in the flue gas. The primary objectives of this project were to: C Achieve a total SO2 removal rate of up to 85 percent. C Demonstrate successful operation of the LIFAC process in a retrofit application in a power plant burning high sulfur U.S. coals. C Produce a dry solid waste suitable for disposal in a landfill. These goals were partially met in this project, which was conducted using medium sulfur coals ranging in sulfur content from 2.0 to 2.8 percent. Coals containing over 3 percent sulfur, which are generally considered high sulfur, were not tested because the unit operation could not be stabilized. However, the LIFAC technology could well be applicable to higher sulfur coals. Overall SO2 removal of about 70 percent was achieved in long term testing; the capability of increasing SO2 removal to 85 percent was inferred from parametric studies but was not actually demonstrated. LIFAC system availability and mechanical operation were very good, and there were no adverse effects on boiler or auxiliaries. The waste product was a dry, stable solid, which was disposed of in a landfill. LIFAC technology has not been further commercialized. In the United States, compliance with SO2 emissions regulations has been achieved primarily through fuel switching or purchase of emission allowances. If a market develops for flue gas desulfurization (FGD) processes with less SO2 emissions reduction capability than conventional wet scrubbing, LIFAC could potentially find a niche.
https://www.google.com/url?sa=t&rct=j&q=&esrc=s&source=web&cd=1&cad=rja&uact=8&ved=0ahUKEwjPg6D6z6TTAhXDPiYKHWEIBf0QFggiMAA&url=https%3A%2F%2Fwww.netl.doe.gov%2FFile%2520Library%2FResearch%2FCoal%2Fmajor%2520demonstrations%2Fcctdp%2FRound3%2FLIFAC%2FLIFAC_PPA.pdf&usg=AFQjCNGQ96GFPNIZynBpwH0aXjWO9x5x0A&bvm=bv.152479541,d.eWE
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COMMENT: Making coal environmentally friendly is a particularly difficult task. This demonstration project, dated 2001, describes an effort to achieve that goal. Whether or not LIFAC proved to be economically viable would require further online research.
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DOE/NETL-2001/1158
Advanced Flue Gas Desulfurization (AFGD) Demonstration Project
A DOE Assessment
August 2001
U.S. Department of Energy
National Energy Technology Laboratory
P.O. Box 880, 3610 Collins Ferry Road
Morgantown, WV 26507-0880
and
P.O. Box 10940, 626 Cochrans Mill Road
Pittsburgh, PA 15236-0940
website: www.netl.doe.gov
Executive Summary
This document serves as a U.S. Department of Energy (DOE) post-project assessment of the Clean Coal Technology (CCT) Round II Advanced Flue Gas Desulfurization (AFGD) Demonstration Project, conducted by Pure Air. Pure Air is a general partnership between Air Products and Chemicals, Inc., and Mitsubishi Heavy Industries America, Inc. In December 1989, Pure Air entered into an agreement to conduct this study, with Northern Indiana Public Service Company (NIPSCO) as the host and cosponsor. DOE provided 42 percent of the total project funding cost of $152 million. The demonstration operations were conducted from June 1992 to June 1995 at NIPSCO’s Bailly Generating Station (units 7 and 8) located in Chesterton, Indiana, to treat the combined flue gases from two boilers with a total nameplate capacity of 616 MWe. The AFGD process accomplishes sulfur dioxide (SO2) removal in a single absorber which performs three functions: prequenching, absorption of SO2, and oxidation to produce gypsum. The performance objectives of this project were to & Remove at least 90-percent SO2, with a target of 95 percent. & Reduce process cost by one-half that of conventional flue gas desulfurization (FGD). & Reduce space requirements. & Produce wallboard-grade gypsum. These performance objectives were met except for process cost which was reduced to 63 percent of conventional FGD cost. The SO2 removal target was exceeded. For the five midwestern bituminous coals tested, with sulfur contents ranging from 2.21 to 4.73 wt%, SO 2 removal efficiency averaged 94 percent, with a maximum of over 98 percent. The demonstration facility was operated for about 26,300 hours, with system availability of 99.5 percent. Over 210,000 tons of wallboard-grade gypsum were produced, having an average purity of 97.2 percent. Costs were estimated for a 500-MWe AFGD unit, using a projected process design which incorporates improvements based on experience gained from the demonstration project. The coal feed is assumed to contain 3 wt% sulfur, and SO 2 emissions are assumed to be reduced by 90 percent. The capital cost is $111/kW. For a 15-year project life, the levelized cost on a current-dollar basis is 5.3 mills/kWh, which is equivalent to $245/ton of SO2 removed. The levelized cost for AFGD is about 63 percent of that for conventional wet limestone desulfurization. This is a significant cost reduction, approaching the target value of 50 percent. Space requirements for AFGD are substantially lower than those for conventional FGD processes. The project received two major awards: the Outstanding Engineering Achievement award, from the National Society of Professional Engineers in 1992; and the Powerplant of the Year award from Power magazine in 1993, for demonstrating advanced limestone FGD technology with innovations in wastewater treatment and gypsum production. The AFGD unit remains in operation at the Bailly Station, where it is performing very well. With increasingly stringent air quality regulations, AFGD technology should be a major contender in a growing market for flue gas cleanup. In addition, the innovative use of gypsum by-product in wallboard manufacture has established a new trend; synthetic gypsum produced at FGD facilities has become the preferred feedstock for wallboard manufacture because its uniform properties simplify manufacturing operations for existing users. https://www.netl.doe.gov/File%20Library/Research/Coal/major%20demonstrations/cctdp/Round2/netl1158-r1.pdf
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COMMENT: This is another item that would require further online research to determine it location on the Technology Readiness scale.
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U.S. Department of Energy
Novel Sorbent to Clean Biogas for Fuel Cell CHP
Improving Desulfurization to Enable Fuel Cell Utilization of Digester Gases
2015
Introduction
With their clean and quiet operation, fuel cells represent a promising means of implementing small-scale distributed power generation. Waste heat from the fuel cell can be harnessed for heating, creating an efficient combined heat and power (CHP) system. If the fuel cell is fueled from a renewable source, its use has the potential to reduce greenhouse gas emissions and natural gas consumption. Derived from agricultural, industrial, and municipal waste streams or from byproducts of industrial processes, opportunity fuels are unconventional fuels that have the potential to become economically viable sources of power generation. One of the most common opportunity fuels, anaerobic digester gas (ADG), is produced from microorganisms’ digestion of biomass. Composed mainly of methane (CH4) and carbon dioxide (CO2), ADG is similar in composition to natural gas. Before ADG can successfully be used in fuel cells, the gas must be cleaned of sulfur compounds that could otherwise lead to decreased performance or even system failure. Fuel cell manufacturers set stringent sulfur limits for feed gas, such as a maximum level of 10 parts per billion by volume (ppbv). However, unreformed ADG may have a sulfur content of up to 150 parts per million by volume (ppmv). A large reduction in ADG sulfur content is required; however, such large reductions cannot be achieved with conventional desulfurization techniques. In particular, existing processes are not effective in removing organic sulfur species, such as dimethyl sulfide, dimethyl disulfide, methanethiol, carbon disulfide, and carbonyl sulfide.
This project is developing a new high-capacity, expendable sorbent to remove sulfur compounds from ADG, thereby producing an essentially sulfur-free biogas meeting the cleanliness requirements of fuel cell power plants. This sorbent will reduce the operating costs of fuel cells consuming ADG and encourage increased use of opportunity fuels. Benefits for Our Industry and Our Nation The desulfurization sorbent developed by this project is an enabling technology that will allow small-scale CHP fuel cell systems to operate on biogas.
Commercialization of this technology has the potential to achieve the following benefits: • A decrease in the net energy intensity of industry by generating power and heat from existing waste streams Full-scale test unit of the developed sorbent-based gas clean-up system. Photo credit TDA Research Inc. • A reduction in greenhouse emissions due to the venting or flaring of digester gases • A reduction in solid waste due to the reduction of sorbent used • A reduced desulfurization cost with extended sorbent replacement cycles and decreased sorbent consumption Applications in Our Nation’s Industry Improved biogas reforming technology will benefit industries that employ anaerobic digesters, particularly those that feed the generated gas into fuel cells. U.S. Environmental Protection Agency analysis from 2014 estimates that the United States has the potential to produce approximately 650 billion cubic feet of biogas per year. This could provide 41 billion kWh of electricity, which is enough energy to power more than 3 million U.S. homes. Anaerobic digesters are used by industries that generate organic waste, including the following: • Wastewater treatment • Municipal and industrial landfills • Food processing • Agriculture, including manure and crop waste, such as dairy farms Project Description The project objective is to develop a new, high-capacity, expendable sorbent to remove sulfur species from anaerobic digester gas, thereby providing a nearly sulfur-free biogas that meets the cleanliness requirements of fuel cell power plants. This sorbent bed operates downstream of a bulk desulfurization system as a polishing bed and removes any residual hydrogen sulfide (H2S) and other organic sulfur species from the biogas. The sorbent is an enabling technology that will allow small-scale fuel cell CHP systems to operate on biogas as an alternative to natural gas.
Barriers • Demonstrating the effectiveness of the sorbent under varying real-world biogas conditions • Scaling up production of the sorbent to a commercial scale • Providing demonstration results and economic analysis to convey the advantages of the new sorbent, as compared to existing alternatives
Pathways TDA Research Inc. (TDA) optimized the key features of the sorbent, such as the concentration of active material and the amount and type of binders used. TDA then increased the batch size of sorbent production over two orders of magnitude to support field demonstrations. TDA performed successful slipstream field demonstrations at two different sites using relatively small sorbent beds. The team is conducting a large-scale demonstration, in Sacramento, CA, desulfurizing all of the biogas for a 600-kilowatt plant. A detailed cost analysis will be performed to assess the economic viability of the new sorbent technology based on field demonstration results. Milestones • Establishing sorbent production capabilities • Screening sorbent variants to determine the best-performing option • Testing the sorbent against alternatives in the laboratory • Testing the sorbent in a slipstream setup at two working digesters • Testing a prototype sorbent bed at a working digester Commercialization This project will lead to the development of a sorbent that is capable of removing complex sulfur compounds from aerobic digester gas at high efficiency. TDA owns the sorbent technology and will license it to its spin-off company SulfaTrap LLC, which will manufacture the product and market it to fuel cell manufacturers and other end users. SulfaTrap currently supplies its desulfurization products to approximately 40% of the world’s installed fuel cell capacity. Both TDA and its project partner FuelCell Energy have successfully commercialized and installed similar technologies in the past. TDA previously developed and commercialized a related sorbent for the desulfurization of natural gas. FuelCell Energy has built numerous fuel cell plants fed by anaerobic digester gas, giving the firm experience in the market and access to operating facilities for demonstrations and testing. Fuel cells are an emerging market with promising growth potential as environmental regulations continue to tighten and the technology’s cost decreases. Also, various tax incentives and grants are available to offset the installation and operation costs of fuel cell plants and anaerobic digesters. Project Partners TDA Research Inc. Wheat Ridge, CO Principal Investigator: Dr. Gokhan Alptekin E-mail: galptekin@tda.com FuelCell Energy Danbury, CT For additional information, please contact Bob Gemmer Technology Manager U.S. Department of Energy Advanced Manufacturing Office Phone: (202) 586-5885 E-mail: Bob.Gemmer@ee.doe.gov
https://energy.gov/sites/prod/files/2015/08/f26/0488-novel_sorbent_to_clean_biogas_factsheet.pdf
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COMMENT: The description makes me think this item would fit into category 3 or 4 …
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3
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prototype, prototype tested
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system function, performance and
reliability tested
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4
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environment tested
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preproduction system environment tested
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Desulfurization Fuel Filter
Ron Rohrbach Honeywell
August 24, 2006
Goal: To develop and demonstrate proof-of-concept for an “on-vehicle”desulfurization fuel filter for diesel engines.
Project Team
•Honeywell Consumer Products Group FRAM
•Marathon Ashland LLC
•Volvo Powertrain(Mack Trucks Inc.)
•Johnson Matthey
•American Waste Industries
Dept of Energy Contract
DOE Contract DE-FC26-02NT41219
Program began April 2002
Fuel Sulfur Removal Filter
In-Going Rationale
•NOx adsorber technology sensitive to sulfur levels in the fuel•Reduction in the number of desulfation events for NOx adsorbers can improve their life•Refineries will face a challenge to achieve economical hydro-desulfurization to achieve levels low enough to not poison NOxadsorbers, 3 ppm or lower.•Reduced fuel sulfur levels make point-of-use sulfur treatment feasible•volume required for an “on-board”sulfur trap is within reason•Pipeline contamination will likely raise sulfur levelsApproach•Develop fuel filter type device as an adsorption bed for sulfur removal.•Integrate sulfur filter maintenance interval to other scheduledmaintenance events
Challenge
The DMDBT looks similar to and behaves like some major components in diesel fuel
Diesel Composition
•20% 1 ring aromatics
•3% 2 ring aromatics (30,000ppm) very similar to DMDBT
•DMDBT is at 10 ppm
3000 to 1 ratio
•Low level polar contaminants in fuel-lubricants, oxidative degradation products and antioxidants
Approaches
•Remove the sulfur contaminant directly (requires high selectivity)
•Convert it into something more easily removed
Create a “chemical hook”
SulfurFilter Benefits•For current NAC operation, periodic sulfur removal is required, via desulfation cycles (DeSOx):-Sulfur is driven off of catalyst by increasing temperature in exhaust-Thermal damage to catalysts can result from high temperature exposure-Significant fuel economy penalty can occur as a result of DeSOxcycles•Fuel sulfur filter will allow interval between DeSOxevents to be extended:-Less thermal damage due to less high temperature exposure-Higher NOxstorage trapping efficiency maintained between DeSOxevents
- Improved fuel economy, compared to operation without fuel sulfur filter
Next Steps
•Reduce size of sorbent bed
-Non-optimized sorbent
-Combinatorial optimization program begun UOP, expected completion Nov 2006
•Deal with lubricity loss issue
-Readditizelubricity additive within filter
•Light duty diesel test
https://energy.gov/sites/prod/files/2014/03/f9/2006_deer_rohrbach.pdf
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COMMENT: With participants like Honeywell, Marathon Ashland, Volvo, Johnson Matthey, and American Waste Industries, this is a project worth exploring. The report is dated 2006, more than 10 years ago, so who knows where it ended up. More online research is indicated.
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April 2013
Catalytic Conversion of Benzothiophene Over a H-ZSM5 Catalyst, Reactivity and a Kinetic Model
Saad A. Al-Bogami
The University of Western Ontario
Supervisor
Prof. Hugo de Lasa
The University of Western Ontario
Graduate Program in Chemical and Biochemical Engineering
A thesis submitted in partial fulfillment of the requirements for the degree in Doctor of Philosophy
ABSTRACT
Nowadays and due to environmental legislations, a world-wide attention has been given towards clean transportation fuels with emphasis on sulfur contents reduction. These efforts on the other hand are challenged by the poor qualities of crude oils. The existing desulfurization technologies such as hydrodesulfurization are not capable to cope with new firm standards. Hence, it is very desirable to develop a catalytic desulfurization process to meet both sulfur limits and refining economics. As one aspect of this objective, it is of great importance to study and comprehend the behavior and reactivity of individual sulfur species present in transportation fuels cuts. Zeolites namely, H-ZSM5 has shown a potential catalyst for a desulfurization process for gasoline fuel range. Acidity and shape selectivity of these zeolites make it viable for such a process eliminating the use of hydrogen. With aiming to light diesel fraction desulfurization, this dissertation provides insights and understanding of benzothiophene sulfur species conversion over a H-ZSM5 zeolite catalyst. The H-ZSM5 particles were dispersed in an inert silica-alumina matrix to diminish possible cracking of diesel component. This catalyst was characterized using standard techniques including: a) NH3-TPD, b) N2 adsorption, c) Particle size distribution, d) X-ray diffraction, e) SEM-EDX, and f) Pyridine FTIR. Catalytic and thermal runs were performed in the CREC Riser Simulator that mimics the industrial FCC unit. Mixtures containing 6 wt% benzothiophene dissolved in n-dodecane were reacted at close to atmospheric pressure, 350°C – 450°C temperatures, and 3, 5, 7 seconds reaction times. Thermal cracking was found to be negligible under the studied reaction conditions. Experimental results from catalytic runs showed a higher benzothiophene conversion over n-dodecane conversion. This was true despite the difference in benzothiophene and n-dodecane molecular sizes. The experimental results of this PhD dissertation are also supported with a molecular dynamics (MD) simulation study that investigates self diffusivity of benzothiophene and n-dodecane in ZSM-5 zeolite. In addition and using the obtained experimental data, a heterogeneous kinetic model is proposed for benzothiophene conversion over H-ZSM5 catalyst. Numerical non- linear regression leads to model parameters estimations with low confidence intervals suggesting the adequacy of this kinetic model.
http://ir.lib.uwo.ca/cgi/viewcontent.cgi?article=2477&context=etd
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COMMENT: Any thesis is, almost by definition, a category 0 or 1 on the Technology Readiness scale.
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Project Proposal
1. Proposal Title: Mercury Adsorption in FGD Wastewater using Waste Char
2. Focus Category: TOXIC SUBSTANCES, WASTEWATER TREATMENT, & WATER QUALITY
3. Keywords: Adsorption, Heavy Metal Removal, FGD wastewater treatment, Activated Carbon
4. Duration: March 1, 2009 through February 28, 2010
5. Federal Funds Requested: $5,000
6. Non-Federal (matching) Funds Pledged: $10,000
7. Principal Investigator
Thomas S. Abia II, EIT
Ph.D. Graduate Student, Biological and Agricultural Engineering (BAEN) Department
Texas A&M University, College Station, TX 77843-2117
(805) 215-8816, tabia@tamu.edu
8. Co-Principal Investigator
Yongheng Huang, PE, Ph.D.
Associate Professor, Biological and Agricultural Engineering (BAEN) Department
Texas A&M University, College Station, TX 77843-2117
(979) 862-8031, yhuang@tamu.edu
Abstract
Acid-gas forming emissions are becoming the target of stringent air regulations and have spurred electric utilities to compensate by installing flue gas desulfurization (FGD) systems (EPRI, 2006). These systems, which are typically wet scrubbers, emit wastewater effluent with high concentrations of fine, suspended heavy metals such as mercury (Hg) and selenium (Se) and consequently negate concurrent tightening wastewater compliance issues (EPRI, 2006). The complexities associated with soluble metal removal, combined with the challenges of utilizing waste by-products, have prompted the development of sustainable and versatile industrial wastewater treatment technology. The objective of this research is to investigate the performance of waste char produced from pyrolysis in removing mercury (Hg) from FGD wastewater. The results of this experiment will produce heavy metal adsorption isotherms for char, define breakthrough capacity, analyze relationship between char quality and adsorption, and compare two types of char for application.
http://twri.tamu.edu/docs/funding/usgs/2009-10/abia-proposal.pdf
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COMMENT: This looks like a category 1 to me.
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Research and Development of an Air Pollution Technology for Simultaneous Desulfurization and Denitrification
ANNUAL REPORT
Prepared for the Natural Sciences and Engineering Research Council of Canada
Lakes Environmental Research Inc., University of Waterloo
Submitted By
Dr. Hesheng Yu, Pollution Equipment Researcher
Lakes Environmental Research Inc., Waterloo, Ontario, CANADA, N2L 3L3
Postdoctoral Fellow, University of Waterloo
Email: yuhesheng@gmail.com
Executive Summary
This proposed project was funded by NSERC Industrial R&D Fellowships (IRDF) program and Ontario-China Research and Innovation Fund (OCRIF) to develop and commercialize a technology that could control multiple air pollutants and emissions in flue gas. It was also supported by in-kind contributions from Lakes Environmental Research Inc. Its research areas include: screening and validation of the continuous process for simultaneous desulfurization and denitrification, gas absorption in a cross-flow hollow fiber membrane contactor (HFMC), mass transfer coefficient of the HFMC, modeling of gas absorption in the cross-flow HFMC, optimization of the selected process based on experimental data and reactor modeling, fundamental study of CO2 absorption into ammonia solutions, and field testing of the validated processes. Drs. Zhongchao Tan and Jesse Thé are the Principle Investigators, and Dr. Hesheng Yu is responsible for the development of research idea, the preparation of proposal, experimental validation, preparation of research plan, instrumentation, methodologies, data collection and analysis, and result delivery. This report covers the work completed during the period between October 1, 2014 and September 30, 2015. Fossil fuel, especially coal, will continue to supply most electricity generation worldwide. Severe air pollution stemming from fuel combustion poses threat to human health and the environment. Effective air pollution control technologies allow us to utilize fossil fuel without causing negative impacts. However, existing flue gas treatment systems are expensive and complicated. Cost-effective air pollution control technology is greatly desired. The combined absorption of SO2 and NOx using wet scrubbing is deemed as a promising alternative to available technologies. Three air pollution control processes including wet scrubbing and liquid treatment have been proposed to effectively address post-combustion flue gas in industrial practices. They are sequential absorption of SO2 and NOx, simultaneous removal of SO2 and NOx, and gas phase pre-oxidation of nitric oxide. Hollow fiber membrane contactor (HFMC) is expected to replace traditional wet scrubber. A continuous wet scrubbing system using simulated flue gas has been established to validate the proposed processes in laboratory. In order to verify the use of HFMC in air pollution control, the absorption of SO2 in a cross flow HFMC using water at 27 oC was performed. Experimental results show that he efficiency of SO2 removal using water in the HFMC remains greater than 99% at QG = 8276 mL/min with liquid-to-gas (L/G) ratio ranging from 0.02 to 0.06. The gas and liquid flow rates can be regulated independently without causing operational failures. The SO2 removal efficiency increases with increasing liquid flow rate and decreasing gas flow rate and SO2 inlet concentration, respectively. The overall volumetric gas phase mass transfer coefficient of the HFMC is in the range of 10 ⋅ , which is higher than those of conventional wet SO2 scrubbers although water is used in HFMC while effective alkaline absorbents are used in the compared reactors. It indicates that the HFMC has advantage in SO2 absorption over conventional absorbers. Furthermore, the liquid side mass transfer coefficient of the HFMC was determined by the absorption of CO2 into pure water. A correlation, 0.28.., was proposed to estimate the liquid-side mass transfer coefficient in the Liqui-Cel HFMC. This correlation will be used in reactor modeling. The regeneration of ammoniacal cobalt(II) solutions is the key to simultaneous absorption of SO2 and NOx using such absorbent. The UVC irradiation was used for the absorbent regeneration because of the well-known photochemistry of cobalt complexes. More importantly, this method will not bring in new contaminants compared with chemical regeneration. Several UVC reactors were tested; however, the regeneration of absorbent was not obvious. Therefore, we moved forward to another proposed process – pre-oxidation of NO. Effective oxidation of inactive NO into soluble NO2 enables us to utilize wet scrubbing for multiple air pollutant control. TiO2-assisted photocatalytic oxidation of NO into NO2 was performed in a simple customized column. Experimental results indicate that TiO2-assisted photocatalytic NO oxidation is effective. The NO conversion efficiency is 53% when the inlet NO concentration is 400 ppm, and O2 is 6%. The temperature for TiO2 thin film preparation and regeneration is critical to the NO conversion efficiency. A calcination temperature of 500-550 oC is deemed suitable. The feasibility of using photocatalytic technology for flue gas treatment on an industrial scale was then analyzed taking account of reaction nature, available UV lamp, equipment materials, scale-up, installation and fouling, and economics. The TiO2-assisted UV technology can effectively remove SO2 and NOx simultaneously based on our experimental results and literature. Mature UV lamp technology and high quality fused quartz materials ensure the application of UV technology in flue gas treatment. The UV technology can be scaled up to large installations, and the quartz material can withstand fine particles and fouling. It would probably possess huge economic advantages over other available methods such as EBFGT. Therefore, it is feasible to use UV technology for de-SOxNOx purpose. A UVC reactor prototype using aluminum materials was then designed. In addition to SO2 and NOx, CO2 is another subject we are interested in. The extension to CO2 absorption enables us to cover the control of all major emissions present in real flue gas, which maximizes the advantages of our proposed technology. The understanding of the kinetics of CO2 absorption into ammonia solutions will well prepare us to be a player in carbon capture and storage (CCS) area. The kinetic information will greatly benefit future reactor design and modeling; therefore, can allow us to include CO2 capture in our proposed technology once funds are available. The kinetics of CO2 absorption into aqueous ammonia solutions were investigated using a DSTR system. It is explicitly determined that the reactive absorption is first order with respect to CO2 but fractional orders between 1.6 – 1.8 with respect to ammonia. The kinetics data can be satisfactorily interpreted by the termolecular mechanism using … In summary, the proposed technologies can effectively control multiple air pollutants and/or emissions in industrial flue gas.
The use of novel HFMC reactor is expected to further enhance the competitiveness of the proposed wet scrubbing technology. The inclusion of CO2 capture will maximize the advantage of our proposed technology. Fundamental studies in mass transfer and kinetics are beneficial to reactor design and process optimization.
http://tan.uwaterloo.ca/publication/ocrif2014-p1.pdf
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COMMENT: Another technology transfer effort, this would appear to fit into one of the following categories …
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3
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prototype, prototype tested
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system function, performance and
reliability tested
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4
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environment tested
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preproduction system environment tested
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BIO-FGD Demonstration Project for Biotechnological Flue Gas Desulfurisation
LIFE95 ENV/NL/000315 (2017)
Contact details:
Project Manager: J.J. VEENEMA
Email: jan.veenema@hccnet.nl
Beneficiaries:
Coordinator nv EPON
Description EPON, the beneficiary, has become ELECTRABEL Nederland, producer of electricity.
Partners BIOSTAR NL KEMA NL AKZO Nobel NL
Project description:
Background
Different techniques are developed and used to reduce air pollutants emissions. From an historical point of view, the dust cleaning systems were the first techniques to reduce air emissions; air filtering with electrostatic filters is a technique which is applied for more than thirty years. A widespread and serious environmental problem is the occurrence of sulphur containing gaseous waste streams such as seen in coal and oil fired power plants. For SO2, the most common technique is the lime(stone)-gypsum process, by which the flue gases are washed with a lime(stone) suspension. The technique used for the reduction of NOx emissions is based on the catalytic reduction with injection of ammonia (SCR). This method requires high investment costs and also presents risks related to the use of ammonia.
Objectives
The objective of the original project was to prove the feasibility and the environmental, technical and cost advantages of a biological flue gas desulphurisation system, called bio-FGD, on a technical scale. It was expected that this new technology would be an alternative to the traditional limestone FGD process which converts sulphur oxides present in the flue gases (SOx) into gypsum. For several reasons, this initial objective was abandoned. At the beginning of 1999, the beneficiary proposed to restructure the project towards biotechnological flue gas denitrification, called BioDeNOx. In the new proposal the system would be combined with standard lime/limestone desulphurisation. It was expected that the proposed combined technology of desulphurization and denitrification could lead to an enormous reduction of investment costs, which would make this technology also applicable for smaller coal based power stations. The main advantages presented by the combined system were: - the BioDeNOx technology is an innovative biological technology that could be implemented in existing desulfurization plants, making use of the existing available equipment and so saving costs; - the BioDeNOx method is based on biological processes and should prove to be less expensive than the traditional selective catalytic reduction (SCR) based methods; - desulphurisation and denitrification are performed in one single treatment unit while the traditional methods require two stages (FGD and SCR).
Results
It has been demonstrated that the simultaneous removal of SO2 and NOx ispossible by utilising and modifying a pilot wet limestone gypsum FGD plant. The basic principle of SO2 removal remains unaffected by the integration of the BioDeNOx process. It has been shown in this project that the NOx solubility can be improved by using a transition metal chelate to bind the NO. Bacteria or biomass are then used to convert this NOx into nitrogen by the consumption of a reducing agent like ethanol. The maximum NOx removal achieved by the project was low (30%) when compared with the results obtained with the SCR method (up to 90%). However, the efficiency is expected to improve significantly in real scale applications due to improved mass transfer efficiency and the decrease of wall effect. Further improvement is also expected from tuning the operational parameters such as optimised droplet size, liquid/gas volume ratio and EDTA concentration. The main advantage of this technology is its low cost. However, until this new technology is validated in real scale, in particular with respect to the operational costs, the benefits remain hypothetical.
http://ec.europa.eu/environment/life/project/Projects/index.cfm?fuseaction=search.dspPage&n_proj_id=1194&docType=pdf
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COMMENT: At pilot scale, this item belongs in one of the two following categories …
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system tested
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production system interface tested
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Reid qualified, system installed
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production system installed and tested
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International Conference on Biological, Civil and Environmental Engineering (BCEE-2014) March 17-18, 2014 Dubai (UAE)
Sulfur Removal of Crude Oil by Ultrasound-Assisted Oxidative Method
Hossein Hosseini and Abdolghader Hamidi
H.Hosseini is with Department of Chemical Engineering, Abadan Branch, Islamic Azad University, Abadan, Iran (phone: +986314460117; e-mail: h.hosseini@iauabadan.ac.ir ).
A.Hamidi is with Omidieh Branch, Islamic Azad University, Omidieh, Iran.
Abstract
Because of high percentage of sulfur in crude oil, sulfur gases are produced and polluted the environment and ultimately can also cause problems during processing. Therefore, in this study a method for the removal of sulfur from sour crude oil using ultrasound-assisted oxidative process has been proposed. This method is actually a combination of oxidative and applying ultrasonic waves to achieve very low sulfur content of crude oil. Keywords—Sulfur removal, Crude Oil, Ultrasound-assisted oxidative.
INTRODUCTION
CRUDE oil is the world's largest and most extensive source of energy that is consumed as vehicle fuels such as gasoline, jet fuel, diesel and so on. As we know crude oil is a sulfur-containing organic and inorganic compound [1]- [2]. The amount of sulfur is one of the most important factors of crude oil’s price. There are a variety of sulfur compounds in crude oil that can be divided into four general categories as follows: Mercaptanes, sulfides, disulfides and thiophenes. Figure 1 shows chemical structure of some of the organic sulfur compounds. R SH R S R` R S S R` S S S S S Thiols Sulfides Disulfides Thiolanes Thiophenes Benzothiophenes Dibenzothiophenes Benzonaphtothiophenes Fig.1. Chemical structure of some of the organic sulfur compounds Sulfur compounds in the refining process are undesirable because it can lead to deactivation of the catalyst and also causes environmental pollution. Presence of sulfur in heavy petroleum fractions leads to emission of SOx which endanger public health. Today, due to stringent environmental regulations there is a strong incentive to reduce sulfur in fuels. In order to control air pollution because of heavy petroleum fractions combustion, most of the countries released a new regulation requiring the use of low-sulfur petroleum fractions. It means that the sulfur content of petroleum fractions used in vehicles be limited to 15 ppm. Hydrodesulfurization process has been a part of refineries for years, but new rules impose a better technology in this field. During the past years, alternative technologies have been studied by many researchers [3]-[4]-[5], among which ultrasound-assisted oxidative desulfurization has found a wide attention. Ultrasound-assisted oxidative desulfurization method for sulfur omission has main benefit compared to other common methods like HDS. Oxidative desulfurization technology as a promising method for deep removal of sulfur under mild conditions has been discussed. This method in comparison to HDS requires much less pressure, temperature and operating costs. This method is based on the oxidation of sulfur compounds and finally the formation of sulfoxides or sulfones. These materials are highly polar and therefore more easily by extraction with solvent or adsorption can remove them from the oil. In the present work, the ultrasound-assisted oxidative desulfurization of crude oil was studied. And also, the factors that affect on this process such as frequency, power, catalyst, temperature and time are investigated.
http://iicbe.org/upload/9150C0314090.pdf
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COMMENT: Based on the description, this seems to be a paper concept, which would place it in category 0, but it might belong in category 1 …
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0
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unproven concept
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basic R&D, paper concept
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1
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proven concept
/ proof of concept
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proof of concept as a paper study or
R&D experiments
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Enzymes are proteins (some may be catalytic RNA) that have unique capacity of speeding up chemical reaction within cells. They accelerate the velocity of the reaction without being altered after the reaction. enzyme catalytic characteristics
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