In that light, here is an item I rec’d thanks to a Google® Alert. Following the description of the item is a TIP on what you might want to do next.
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US 2018/0296969
SULFUR REMOVAL SYSTEM
Apr 12, 2017- KING FAHD UNIVERSITY OF PETROLEUM AND MINERALS
A sulfur removal system including a first reactor and a second reactor that are located in series to one another each having an adsorbent that includes cobalt and copper on an activated carbon support, a method of desulfurizing a sulfur-containing hydrocarbon stream via the sulfur removal system, and a method of making the adsorbent. Various embodiments of the sulfur removal system, the desulfurizing method, and the method of making the adsorbent is also provided.
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Description
STATEMENT OF FUNDING ACKNOWLEDGEMENT
The support provided by King Abdulaziz City for Science and Technology (KACST) through the Science & Technology Unit at King Fahd University of Petroleum & Minerals (KFUPM) for funding through a project no. 13-PET393-04 as part of the National Science, Technology and Innovation Plan is acknowledged.
BACKGROUND OF THE INVENTION
Technical Field
The present invention relates to a sulfur removal system with a first and a second reactor and an adsorbent that includes cobalt and copper on an activated carbon support.
DESCRIPTION OF THE RELATED ART
The “background” description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description which may not otherwise qualify as prior art at the time of filing, are neither expressly or impliedly admitted as prior art against the present invention.
Hydro-desulfurization is a common method of desulfurization that is widely used in refineries. This method, however, requires a high temperature, a high pressure, and a large catalyst volume [C. Song, Fuel processing for low-temperature and high-temperature fuel cells: challenges, and opportunities for sustainable development in the 21st century, Catal. Today 77 (2002) 17-49; D. D. Whitehurst, T. Isoda, and I. Mochida, Present State of the Art and Future Challenges in the Hydrodesulfurization of Polyaromatic Sulfur Compounds, Elsevier Masson SAS 42 (1998) 345-471; R. Shafi and G. J. Hutchings, Hydrodesulfurization of hindered dibenzothiophenes: an overview, Catal., Today 59 (2000), 423-422]. Therefore, adsorptive desulfurization has been considered as an alternative desulfurization technique that provides relatively mild operating conditions and higher selectivity for thiophenic compounds compared to hydro-desulfurization techniques. In addition, adsorptive desulfurization can provide nearly 100% sulfur removal when a suitable adsorbent is used [I. Ahmed, S. H. Jhung, Composites of metal-organic frameworks: Preparation and application in adsorption, Mater. Today 17 (2014) 136-146; J. M. Palomino, D. T. Tran, A. R. Kareh, C. A. Miller, J. M. V Gardner, H. Dong, S. J. Oliver, Zirconia-silica based mesoporous desulfurization adsorbents, J. Power Sources. 278 (2015) 141-148].
Selecting a suitable adsorbent is important for an efficient adsorptive desulfurization process. It has been shown that metal oxides are among good sulfur adsorbents that are functional at high temperatures. Various metal oxides have been reported as efficient sulfur adsorbents due to their high affinity to sulfur. Exemplary metal oxides include Zn, Mn, Cu, Co, Ni, Cr, Ca, and Fe [H. F. Garces, H. M. Galindo, L. J. Garces, J. Hunt, A. Morey, S. L. Suib, Low temperature H2S dry-desulfurization with zinc oxide, Microporous Mesoporous Mater. 127 (2010) 190-197; J. Bin Chung, J. S. Chung, Desulfurization of H2S using cobalt-containing sorbents at low temperatures, Chem. Eng. Sci. 60 (2005) 1515-1523; H. F. Garces, A. E. Espinal, S. L. Suib, Tunable shape microwave synthesis of zinc oxide nanospheres and their desulfurization performance compared with nanorods and platelet-like morphologies for the removal of hydrogen sulfide, J. Phys. Chem. C. 116 (2012) 8465-8474; M. Flytzani-Stephanopoulos, M. Sakbodin, Z. Wang, Regenerative Adsorption and Removal of H2S from Hot Fuel Gas Streams by Rare Earth Oxides, Science, 312 (2006) 1508-1510; E. Richter, Chemical Reactions as a Means of Separation: Sulfur Removal, Chemie Ing. Tech. 50 (1978) 698-698; T. A. Saleh, G. I. Danmaliki, Adsorptive desulfurization of dibenzothiophene from fuels by rubber tires-derived carbons: Kinetics and isotherms evaluation, Process Safety and Environmental Protection 102 (2016) 9-19; G. I. Danmaliki, T. A. Saleh, Influence of conversion parameters of waste tires to activated carbon on adsorption of dibenzothiophene from model fuels, Journal of Cleaner Production, 117 (2016) 50-55; T. A. Saleh, G. I. Danmaliki, Influence of acidic and basic treatments of activated carbon derived from waste rubber tires on adsorptive desulfurization of thiophenes, Journal of the Taiwan Institute of Chemical Engineers, 60 (2016) 460-468; T. A. Saleh, The influence of treatment temperature on the acidity of MWCNT oxidized by HNO3 or a mixture of HNO3/H2SO4, Applied Surface Science, 257 (2011) 7746-7751]. On the other hand, various methods have been developed to enhance the performance of an adsorptive desulfurization process. Accordingly, researchers have investigated the performance of an adsorptive desulfurization process by doping metals or metal oxides onto sulfur adsorbents. For example, Ca—Ba, Zinc ferrite (ZnxFe3-xO4), Cu—Cr—O and Cu—Ce—O adsorbents have been successfully utilized in an adsorptive desulfurization process at high temperature [M. Stemmler, A. Tamburro, M. Muller, Laboratory investigations on chemical hot gas cleaning of inorganic trace elements for the ‘UNIQUE’ process, Fuel, 108 (2013) 31-36; R. E. Anala, D. W. Marsh, Characterization and Long-Range Reactivity of Zinc Ferrite in High-Temperature Desulfurization Processed, Ind. Eng. Chem. Res. 30, (1991) 55-60; Z. Li, M. Flytzani-stephanopoulos, Cu—Cr—O and Cu—Ce—O Regenerable Oxide Sorbents for Hot Gas Desulfurization, 36 (1997) 187-196]. In a separate study, these metals or metal oxides have been placed on a surface of one or more adsorptive supports e.g. silica, alumina, zeolite, or activated carbon in order to boost the number of active adsorptive sites of the adsorbents. Among these adsorptive supports, activated carbon revealed good surface characteristics with large pore volumes [K. S. Triantafyllidis, E. A. Deliyanni, Desulfurization of diesel fuels: Adsorption of 4,6-DMDBT on different origin and surface chemistry nanoporous activated carbons, Chem. Eng. J. 236 (2014) 406-414]. In addition, an activated carbon support can be treated in an acidic or a basic solution to generate a surface modified support that has active adsorptive sites [C. Y. Yin, M. K. Aroua, W. M. Daud, Review of modifications of activated carbon for enhancing contaminant uptakes from aqueous solutions, Sep. Purif. Technol. 52 (2007) 403-415]. In a recent study, an activated carbon support has been impregnated with Pd, Al, and Fe. The resulting adsorbent revealed promising results in an adsorptive desulfurization process [A. Lopes, A. Scheer, G. Silva, C. Yamamoto, Pd-Impregnated activated carbon and treatment acid to remove sulfur and nitrogen from diesel, Materia (Rio Janeiro) 21 2016 407-415; S. A. Ganiyu, K. Alhooshani, K. O. Sulaiman, M. Qamaruddin, I. A. Bakare, A. Tanimu, T. A. Saleh, Influence of aluminium impregnation on activated carbon for enhanced desulfurization of DBT at ambient temperature: Role of surface acidity and textural properties, Chem. Eng. J. 303 (2016) 489-500; J. X. Guo, S. Shu, X. L. Liu, X. J. Wang, H. Q. Yin, Y. H. Chu, Influence of Fe loadings on desulfurization performance of activated carbon treated by nitric acid, Environ. Technol. 3330 (2016) 1-11].
In view of the forgoing, one objective of the present invention is to provide a sulfur removal system that utilizes an adsorbent to effectively remove sulfur compounds via an adsorptive desulfurization process at room temperature and atmospheric pressure. The adsorbent includes cobalt and copper on an activated carbon support.
BRIEF SUMMARY OF THE INVENTION
According to a first aspect, the present disclosure relates to a sulfur removal system including i) a first reactor including a) a first vessel having a first internal cavity with a first adsorbent bed that contains a first adsorbent, b) a first inlet located proximal to a bottom of the first vessel, c) a first outlet located proximal to a top of the first vessel, ii) a second reactor including a second vessel having a second inlet, a second outlet, and a second internal cavity with a second adsorbent bed that contains a second adsorbent, wherein the first and the second adsorbents comprise cobalt and copper on an activated carbon support, wherein the first adsorbent bed has a cross-sectional area that is substantially the same as a cross-sectional area of the first vessel, and wherein the second inlet is fluidly connected to the first outlet via a connecting line.
In one embodiment, the first and the second adsorbents are substantially the same.
In one embodiment, the system further includes a lower mesh structure located in the first internal cavity and proximal to the bottom of the first vessel and an upper mesh structure located in the first internal cavity and proximal to the top of the first vessel, defining the first adsorbent bed.
In one embodiment, the first adsorbent has a particle size in the range of 0.5 to 10 mm, and wherein the lower and the upper mesh structures have a mesh size of less than 0.5 mm.
In one embodiment, the first reactor is a fluidized-bed reactor.
In one embodiment, the second reactor is a fixed-bed reactor.
In one embodiment, the second inlet is located proximal to a top of the second vessel and the second outlet is located proximal to a bottom of the second vessel.
In one embodiment, the second inlet is located proximal to a bottom of the second vessel and the second outlet is located proximal to a top of the second vessel.
In one embodiment, the system further includes a liquid reservoir located upstream of and fluidly connected to the first inlet via a solvent line, wherein the liquid reservoir is configured to deliver a solvent to the first and the second internal cavities to regenerate the first and the second adsorbents.
According to a second aspect, the present disclosure relates to a method of desulfurizing a sulfur-containing hydrocarbon stream with the sulfur removal system, involving i) delivering the sulfur-containing hydrocarbon stream to the first inlet and contacting the sulfur-containing hydrocarbon stream with the first adsorbent to form a partially desulfurized hydrocarbon stream, ii) delivering the partially desulfurized hydrocarbon stream to the second inlet and contacting the partially desulfurized hydrocarbon stream with the second adsorbent to form a desulfurized hydrocarbon stream.
In one embodiment, the sulfur-containing hydrocarbon stream is contacted with the first adsorbent at a temperature of 15 to 35° C. and a pressure of 0.9 to 1.1 atm.
In one embodiment, the partially desulfurized hydrocarbon stream is contacted with the second adsorbent at a temperature of 15 to 35° C. and a pressure of 0.9 to 1.1 atm.
In one embodiment, the sulfur-containing hydrocarbon stream comprises at least one sulfur compound selected from the group consisting of a thiophene, a benzothiophene, a dibenzothiophene, a methyl benzothiophene, a methyl dibenzothiophene, and a dimethyl dibenzothiophene.
In one embodiment, a concentration of sulfur compounds in the sulfur-containing hydrocarbon stream is at least 50 ppm, and wherein a concentration of sulfur compounds in the desulfurized hydrocarbon stream is no more than 5 ppm.
In one embodiment, the sulfur removal system further includes a liquid reservoir located upstream of and fluidly connected to the first inlet via a solvent line, and the method further involves delivering a solvent to the first inlet to regenerate the first adsorbent and the second inlet to regenerate the second adsorbent.
In one embodiment, the first adsorbent is regenerated within the first reactor and the second adsorbent is regenerated within the second reactor.
In one embodiment, the method further involves delivering an inert gas to the first inlet to evaporate the solvent, after delivering the solvent.
In one embodiment, the inert gas is nitrogen gas with a temperature in the range of 150 to 350° C., which is delivered with a flow rate of 0.02 to 5 L/min.
According to a third aspect, the present disclosure relates to a method of making an adsorbent, which comprises cobalt and copper on an activated carbon support. The method involves i) mixing activated carbon particles with an aqueous solution comprising at least one of ethanol, diethylene glycol, and sodium diacetate to form a first suspension, ii) mixing a cobalt-containing solution with the first suspension and refluxing to form cobalt-containing activated carbon particles, iii) filtering and drying the cobalt-containing activated carbon particles and mixing the same with the aqueous solution to form a second suspension, iv) mixing and refluxing a copper-containing solution with the second suspension to form the adsorbent.
In one embodiment, the method further involves i) isothermally heating a rubber at a temperature of 250 to 550° C. to form a char, ii) treating the char with an oxidizing agent to remove organic impurities, iii) isothermally heating the char at a temperature of 400 to 900° C., iv) treating the char with an acid solution to form the activated carbon particles, prior to mixing the activated carbon particles with the aqueous solution.
In one embodiment, the cobalt-containing solution is cobalt acetate dissolved in deionized water.
In one embodiment, the copper-containing solution is copper nitrate dissolved in deionized water.
The foregoing paragraphs have been provided by way of general introduction, and are not intended to limit the scope of the following claims. The described embodiments, together with further advantages, will be best understood by reference to the following detailed description taken in conjunction with the accompanying drawings.
source: https://patents.justia.com/patent/20180296969
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TIP: Google® king fahd patents to see what else King Fahd University of Petroleum and Minerals is exploring.
Remember, as implied in its name, King Fahd University is laser focused on research that enables and enhances the production of hydrocarbons and the processing of same. So even when that patent doesn’t seem to involve sulfur or desulfurization or dibenzothiophene, it may be of interest.
Also remember that, even if a patent does not interest you, it may interest a colleague. Let your colleagues in on your secret.
Here is a selection of recent King Fahd patents …
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Patents Assigned to King Fahd University of Petroleum and Minerals
Moving part image partitioning for walking gait identification
Patent number: 10115006
Abstract: Described herein is an apparatus and method for gait recognition. The apparatus includes circuitry that is configured to receive a gait sequence including a predetermined number of image frames of a subject. The received gait sequence is processed to generate a gait-energy-image (GEI). A plurality of Gabor filter responses is computed by convoluting the generated GEI with a bank of Gabor filters, wherein the filter bank includes a first predetermined number of unique scales, and a second predetermined number of unique orientations. Further, the circuitry is configured to partition, each Gabor filter response of the computed plurality of Gabor filter responses, into a predetermined number of overlapping regions and extract, a predetermined number of statistical features only from the overlapping regions, the extracted statistical features corresponding to texture consent of the subject. The circuitry eventually recognizes the subject based on a classification of the extracted statistical features.
Type: Grant
Filed: June 14, 2018
Date of Patent: October 30, 2018
Assignee: King Fahd University of Petroleum and Minerals
Inventors: Amer Ghazi Abdullah Binsaadoon, El-Sayed M. El-Alfy
Acceleration measurement apparatus
Patent number: 10114145
Abstract: An apparatus and method for measuring a local acceleration of gravity includes releasing a ferrous rod having a regular alternating pattern of reflective and non-reflective portions on a surface thereof from an electromagnetic holder so that the rod falls with a substantially vertical acceleration and substantially no angular velocity about a center of mass of the rod. The falling rod is illuminated with a light emitting diode (LED) configured to emit infrared (IR) light, and IR light emitted by the LED and reflected by the falling rod is detected with a photodiode. A two-state signal is generated corresponding to an illumination state of the photodiode by the reflected IR light. Times of transitions between the two states in the generated signal are calculated to determine kinematic data, and the kinematic data is fitted to a predetermined curve to calculate a local acceleration of gravity.
Type: Grant
Filed: June 5, 2018
Date of Patent: October 30, 2018
Assignee: King Fahd University of Petroleum and Minerals
Inventors: Sohaib Abdelazem, Watheq Al-Basheer
Systems and methods for an optical logic device
Patent number: 10114270
Abstract: An optical logic device includes a distributed feedback laser configured to generate a first signal corresponding to distributed feedback laser output signal, the first signal being at a first wavelength. The device further includes a bandpass filter having a center frequency corresponding to the first wavelength. Additionally, the device can include an optical circulator having a first port coupled to a logic device input signal, a second port coupled to the first signal, and a third port coupled to the bandpass filter, wherein when the logic device input signal has a power above a predetermined threshold and there is a wavelength difference between the first wavelength and an input wavelength of the logic device input signal, a suppression of the first signal occurs.
Type: Grant
Filed: September 2, 2016
Date of Patent: October 30, 2018
Assignee: King Fahd University of Petroleum and Minerals
Inventor: Khurram Karim Qureshi
Flow cell for batch and continuous simultaneous electrochemical and EPR measurements and a method thereof
Patent number: 10114101
Abstract: A flow cell and a method for batch and continuous simultaneous electrochemical (EC) and electron paramagnetic resonance (EPR) measurements. The flow cell includes first and second tubes with hollow interiors and the first tube is removably connected to first and second tube assemblies. The interior of the second tube contains first ends of first and second electrodes and a solution comprising an analyte. When a voltage is applied to the second electrode, the analyte undergoes a reduction or an oxidation process to generate radicals, which in turn, give rise to EPR signals.
Type: Grant
Filed: March 25, 2016
Date of Patent: October 30, 2018
Assignee: King Fahd University of Petroleum and Minerals
Inventors: Mohamed Aly Morsy, Abdel-Nasser Metwally Kawde
Method for hydrophobicizing a copper-tin alloy
Patent number: 10112264
Abstract: A method of treating a metallic surface comprising a copper alloy, such as phosphor bronze, whereby the metallic surface is ablated by directing a laser beam with a diameter of 200-400 ?m produced by a CO2 laser with a pulse frequency of 1200-1800 HZ onto the metallic surface, and a N2 assist gas is concurrently applied with a pressure of 550-650 KPa co-axially with the laser beam to form an ablated metallic surface comprising microgrooves with Cu3N present on a surface of the microgrooves, wherein the ablated metallic surface has a higher surface hydrophobicity than the metallic surface prior to the ablating.
Type: Grant
Filed: February 9, 2018
Date of Patent: October 30, 2018
Assignee: King Fahd University of Petroleum and Minerals
Inventors: Bekir Sami Yilbas, Haider Ali
Fluidized-bed cracking of butene to form propylene and ethylene
Patent number: 10112190
Abstract: A method of producing propylene and ethylene from a butene-containing hydrocarbon stream by cracking olefin compounds in the butene-containing hydrocarbon stream in the presence of a core-shell ZSM catalyst, wherein the core-shell ZSM catalyst comprises a ZSM-5 core and a silica shell disposed thereon. Various embodiments of the method of producing propylene and ethylene, and the method of making the core-shell ZSM catalyst are also provided.
Type: Grant
Filed: June 2, 2018
Date of Patent: October 30, 2018
Assignee: King Fahd University of Petroleum and Minerals
Inventors: Sulaiman Al-Khattaf, Palani Arudra, Amr Abdalla
Trans-metallated MOF catalyst
Patent number: 10112189
Abstract: A metal organic framework comprising zinc (II) ions and second metal ions, such as iron (II) ions, cobalt (II) ions, and copper (II) ions as nodes or clusters and coordinated 1,3,5-benzenetricarboxylic acid struts or linkers between them forming a porous coordination network in the form of polyhedral crystals that are isostructural to HKUST-1. Transmetallation processes for producing the metal organic frameworks, as well as methods for applications of the metal organic frameworks as catalysts, specifically catalysts for the oxidation of cyclic hydrocarbons, such as toluene, cyclohexane, and methylcyclohexane.
Type: Grant
Filed: April 30, 2018
Date of Patent: October 30, 2018
Assignee: King Fahd University of Petroleum and Minerals
Inventors: Abiola Azeez Jimoh, Abdul Malik Peedikakkal
Method for cracking butene
Patent number: 10112191
Abstract: A method of producing propylene and ethylene from a butene-containing hydrocarbon stream by cracking olefin compounds in the butene-containing hydrocarbon stream in the presence of a core-shell ZSM catalyst, wherein the core-shell ZSM catalyst comprises a ZSM-5 core and a silica shell disposed thereon. Various embodiments of the method of producing propylene and ethylene, and the method of making the core-shell ZSM catalyst are also provided.
Type: Grant
Filed: June 2, 2018
Date of Patent: October 30, 2018
Assignee: King Fahd University of Petroleum and Minerals
Inventors: Sulaiman Al-Khattaf, Palani Arudra, Amr Abdalla
source: https://patents.justia.com/assignee/king-fahd-university-of-petroleum-and-minerals
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