What’s the quickest way to determine if a patent is of interest to you? Depends on your purpose. This tip sheet may help you decide which section of a patent to focus on.
A previous post (http://desulf.blogspot.com/2020/03/starting-down-startup-path-part-6-of.html) offers tips on how to quickly review patents to find those that fill your research needs.
The authors agree that the patent abstract is not that useful. They differ as to whether the CLAIMS section or the SUMMARY section is most useful.
Now, I am by no means an expert in patent searching. But I think it depends on your purpose. For those of you considering filing a new patent, or disputing an existing patent, the CLAIMS section may be your first stop.
For science researchers trying to determine their next steps, the SUMMARY section may be the better choice.
So, for fun, I searched for patents using the Google® search term DIBENZOTHIOPHENE. I extracted the Abstract, Claims, and Summary of several of the search results. They are reproduced below, so you can see how the three patent sections compare.
Maybe it will help you decide what to focus on as you conduct your patent search.
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Comparison: Patent Abstract, Claims, and Summary
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Selective liquid-liquid extraction of oxidative desulfurization reaction products
Inventors: Emad Naji Al-Shafei, Esam Zaki Hamad,
Current Assignee: Saudi Arabian Oil Co
Abstract
The present invention provides selective extraction of sulfoxides, or sulfoxides in combination with sulfones, from hydrocarbon mixtures containing these compounds. A significant advantage of the invention is that oxidation products resulting from oxidative desulfurization of hydrocarbon feedstocks are selectively extracted with minimum co-extraction of non-oxidized products such as valuable hydrocarbon fuel components.
US20130075305A1
Claims (38)
We claim:
1. A process for extracting sulfoxidation reaction products from hydrocarbon fractions containing sulfoxidation reaction products while minimizing co-extraction of hydrocarbons including aromatic hydrocarbons, comprising:
contacting a hydrocarbon fraction containing sulfoxidation reaction products with a selective solvent formulation comprising an aqueous solution having a concentration of about 2.5 weight % to about 70 weight % of a polar organic solvent, the polar organic solvent selected from the group consisting of acetone, methanol, acetonitrile, acetic acid, formic acid and combinations comprising at least two of the foregoing polar organic solvents, wherein the concentration of the aqueous solution is selected to maximize extraction of a target sulfoxidation reaction product and minimize co-extraction of unoxidized organosulfur compounds and hydrocarbons including aromatic hydrocarbons.
2. The process as in claim 1, wherein the concentration of the aqueous solution is about 30 weight % to about 70 weight % of polar organic solvent, and the target sulfoxidation reaction product includes
a. one or more sulfoxidation products derived from aromatic organosulfur compounds including thiophene, benzothiophene, napthothiophene, dibenzothiophene, naptho-benzo-thiophene, or alkyl and dialkyl derivatives of one or more of thiophene, benzothiophene, napthothiophene, dibenzothiophene, or naptho-benzo-thiophene; or
b. a combination of sulfoxides and sulfones.
3. The process as in claim 1, wherein the concentration of the aqueous solution is about 2.5 weight % to about 50 weight % of acetone.
4. The process as in claim 3, wherein the concentration of the aqueous solution is about 2.5 weight % to about 20 weight % of acetone, and wherein the target compounds for extraction are non-bulky sulfoxide products.
5. The process as in claim 3, wherein the concentration of the aqueous solution is about 20 weight % to about 50 weight % of acetone, and wherein the target compounds for extraction are bulky sulfoxide products.
6. The process as in claim 1, wherein the concentration of the aqueous solution is about 2.5 weight % to about 70 weight % of methanol.
7. The process as in claim 6, wherein the concentration of the aqueous solution is about 10 weight % to about 30 weight % of methanol, and wherein the target compounds for extraction are non-bulky sulfoxide products.
8. The process as in claim 6, wherein the concentration of the aqueous solution is about 30 weight % to about 70 weight % of methanol, and wherein the target compounds for extraction are bulky sulfoxide products.
9. The process as in claim 1, wherein the concentration of the aqueous solution is about 2.5 weight % to about 60 weight % of acetonitrile.
10. The process as in claim 9, wherein the concentration of the aqueous solution is about 5 weight % to about 30 weight % of acetonitrile, and wherein the target compounds for extraction are non-bulky sulfoxide products.
11. The process as in claim 9, wherein the concentration of the aqueous solution is about 20 weight % to about 40 weight % of acetonitrile, and wherein the target compounds for extraction are bulky sulfoxide products.
12. The process as in claim 9, wherein the concentration of the aqueous solution is about 40 weight % to about 55 weight % of acetonitrile, and the target sulfoxidation reaction product is a combination of sulfoxides and sulfones.
13. The process as in claim 1, wherein the concentration of the aqueous solution is about 2.5 weight % to about 70 weight % of acetic acid.
14. The process as in claim 13, wherein the concentration of the aqueous solution is about 2.5 weight % to about 20 weight % of acetic acid, and wherein the target compounds for extraction are non-bulky sulfoxide products.
15. The process as in claim 13, wherein the concentration of the aqueous solution is about 20 weight % to about 40 weight % of acetic acid, and wherein the target compounds for extraction are bulky sulfoxide products.
16. The process as in claim 13, wherein the concentration of the aqueous solution is about 30 weight % to about 70 weight % of acetic acid, and the target sulfoxidation reaction product is a combination of sulfoxides and sulfones.
17. The process as in claim 1, wherein the concentration of the aqueous solution is about 2.5 weight % to about 70 weight % of formic acid.
18. The process as in claim 17, wherein the concentration of the aqueous solution is about 2.5 weight % to about 30 weight % of formic acid, and wherein the target compounds for extraction are non-bulky sulfoxide products.
19. The process as in claim 17, wherein the concentration of the aqueous solution is about 30 weight % to about 70 weight % of formic acid, and wherein the target compounds for extraction are bulky sulfoxide products.
20. The process as in claim 17, wherein the concentration of the aqueous solution is about 50 weight % to about 70 weight % of formic acid, and the target sulfoxidation reaction product is a combination of sulfoxides and sulfones.
21. The process as in claim 1, wherein the concentration of the aqueous solution is about 5 weight % to about 30 weight % of acetonitrile and about 5 weight % to about 30 weight % of formic acid.
22. The process as in claim 1, wherein the concentration of the aqueous solution is about 5 weight % to about 30 weight % of acetic acid and about 5 weight % to about 30 weight % of acetone.
23. The process as in claim 1, wherein the concentration of the aqueous solution is about 5 weight % to about 30 weight % of acetonitrile and about 5 weight % to about 30 weight % of acetone.
24. The process as in claim 1, wherein the activity coefficient of the target sulfoxidation reaction product is less than about 16.5 and the activity coefficient of the aromatic hydrocarbons is greater than about 16.5.
25. The process as in claim 1, wherein the activity coefficient of the target sulfoxidation reaction product is less than about 16.5 and the activity coefficient of unoxidized organosulfur compounds is greater than about 16.5.
26. A sulfoxidation process comprising:
reactively sulfoxidating a hydrocarbon fraction containing organosulfur compounds to produce sulfoxidation reaction products;
extracting sulfoxidation products using an extraction solvent according to the process of claim 1; and
recovering a hydrocarbon product of reduced sulfur content.
27. The sulfoxidation process as in claim 26, further comprising recovering at least a portion of the extraction solvent by heating, whereby the target sulfoxidation reaction product is removed.
28. The sulfoxidation process as in claim 27, wherein the target sulfoxidation reaction product is removed in liquid form.
29. The sulfoxidation process as in claim 27, wherein the target sulfoxidation reaction product is precipitated in solid form.
30. The sulfoxidation process as in claim 26, further comprising polishing the hydrocarbon product of reduced sulfur content.
31. The sulfoxidation process as in claim 30, wherein polishing comprises an aqueous polishing process.
32. The sulfoxidation process as in claim 26, wherein sulfoxidation and extraction occur in the same reaction unit.
33. The sulfoxidation process as in claim 26, wherein sulfoxidation occurs in a reaction unit, further comprising feeding the effluent from the reaction unit comprising treated hydrocarbon and the sulfoxidation reaction products into an extraction unit for extracting sulfoxidation products.
34. The sulfoxidation process as in claim 26, wherein sulfoxidation is effected by an oxidation process selected from the group consisting of photooxidation, photochemical oxidation, ozonation, ionic liquid oxidation, electro chemical oxidation, bio-desulfurization, oxidation by hydrogen peroxide, oxidation by organic peracid, oxidation by peroxomonophosphoric acid, oxidation by nitrogen oxides, oxidation by nitric acid, and a combination of any of the foregoing oxidation processes.
35. The sulfoxidation process as in claim 26, wherein sulfoxidation is conducted at temperatures of about 0° C. to about 40° C.
36. The sulfoxidation process as in claim 26, wherein sulfoxidation is conducted at atmospheric pressure.
37. The sulfoxidation process as in claim 26, wherein sulfoxidation is conducted at temperatures of about 0° C. to about 40° C. and atmospheric pressure.
38. A method of determining an extraction solvent composition for extracting sulfoxidation reaction products from a hydrocarbon fraction containing sulfoxidation reaction products comprising:
qualitatively analyzing the hydrocarbon fractions containing sulfoxidation reaction products to determine the type of sulfoxidation reaction products, and the type of aromatic hydrocarbons and/or the type of non-aromatic hydrocarbons;
selecting as a target sulfoxidation reaction product one or more sulfoxides or a combination of one or more sulfoxides and one or more sulfones;
determining the activity coefficient ln γ of a range of extraction solvent compositions for the target sulfoxidation reaction product and at least one type of aromatic or non-aromatic hydrocarbon, the extraction solvent compositions within the range of extraction solvent compositions comprising an aqueous solution having a concentration of about 2.5 weight % to about 70 weight % by weight polar organic solvent in water, the polar organic solvent selected from the group consisting of acetone, methanol, acetonitrile, acetic acid, formic acid and combinations comprising two or more of acetone, methanol, acetonitrile, acetic acid and formic acid;
selecting an extraction solvent composition having an activity coefficient of less than about 16.5 for the target sulfoxidation reaction product that maximizes extraction of the target sulfoxidation reaction product, and an activity coefficient greater than about 16.5 for the at least one type of aromatic or non-aromatic hydrocarbon that minimizes co-extraction of the at least one type of aromatic or non-aromatic hydrocarbon.
SUMMARY OF THE INVENTION
[0016]
The process described herein is directed to selective extraction of sulfoxides, or sulfoxides in combination with sulfones, from hydrocarbon mixtures containing these compounds. A significant advantage of the process described herein is that oxidation products resulting from oxidative desulfurization of hydrocarbon feedstocks are selectively extracted with minimum co-extraction of non-oxidized products such as valuable hydrocarbon fuel components.
[0017]
According to the process described herein, a selective solvent formulation, which, as used herein refers to a solvent formulation having particular solubility to the target oxidation by-product, is brought into contact with a hydrocarbon mixture during or after oxidation reactions that produce sulfoxides and/or sulfones. In certain embodiments, the hydrocarbon mixture containing sulfoxides and/or sulfones is contacted with the selective solvent formulation under mild conditions, i.e., at a temperature in the range of from about 0° C. to about 40° C., and a pressure in the range of from about 10 kPa to about 205 kPa, in certain embodiments about 95 kPa to about 105 kPa, and in further embodiments about 101 kPa.
[0018]
The liquid-liquid extraction process can be carried out in a batch reactor, a continuous flow reactor, a tubular flow reactor, and/or in a liquid-liquid separator. An advantage of the process described herein compared to prior art extraction processes relates to the use of a selective solvent formulation that minimizes co-extraction of valuable hydrocarbon compounds during the liquid-liquid extraction step.
[0019]
Another advantage of the process described herein is facilitating extraction of sulfoxides, and/or sulfoxides combined with sulfones, resulting from oxidation of hydrocarbon feeds by using the selective solvent formulation, thereby reducing the complexity and overall number of extractive steps. In conventional approaches, pure solvent is required, and necessary steps include storage of large quantities of highly flammable solvent, recycling of large quantities of solvent with an evaporation unit and distillation unit with multiple stages of cooling towers with associated tanks to segregate the sulfoxides and sulfones from the co-extraction of aromatics along with untreated organosulfur compounds. However, the process described herein is selective to extract the oxidized sulfur, and the solvent is recycled and separated from oxidized sulfur. In addition, polishing of oxidant material can be accomplished by flashing water after extraction, which can eliminate acid, peroxide or solvent remaining in treated stream. Therefore, by employing the selective solvent formulations of the process described herein, the total sulfur will be reduced in a shorter time while minimizing the co-extraction of other valuable hydrocarbons.
[0020]
A further advantage of certain embodiments of the process described herein is the reduction of the oxygen required and a reduction in the oxidation reaction time by promoting formation of sulfoxides rather than increasing the oxidation to the subsequent step of sulfone formation. Sulfoxides can be formed using existing oxidation methods of photo-oxidation, photochemical oxidation, ozonation, ionic liquid oxidation, electro-chemical oxidation, bio-desulfurization, or contacting with hydrogen peroxides, organic peracids, peroxomonophosphoric acid, nitrogen oxides and/or nitric acid. In general, sulfoxides are more easily extracted than sulfones. Sulfoxides alone can be extracted with less solvent formulation. Under oxidation conditions using peroxides as the oxidation agent at mild operating conditions such as temperatures of about 30° C. to about 40° C., both sulfoxides and sulfones are formed.
[0021]
With appropriate oxidation conditions and/or catalysts, sulfoxide production can be favored. Using certain solvents, the formulation concentration can be increased to extract both sulfoxides and sulfones while minimizing or eliminating co-extraction of untreated organosulfur compounds.
[0022]
As used herein, the term “sulfoxide products” refers to sulfoxides resulting from oxidation of organosulfur compounds and “sulfoxidation products” refers to the combination of sulfoxides and sulfones resulting from oxidation of organosulfur compounds.
[0023]
Also as used herein, the term “bulky sulfoxide products” refers to sulfoxides having more than 12 carbon atoms, thiophenes with more than 4 carbon atoms, and sulfoxidation products of polyaromatic organosulfur compounds such as benzothiophenes, napthothiophenes, dibenzothiophenes, naptho-benzo-thiophene and alkyl and dialkyl derivatives of any of the aforementioned aromatic organosulfur compounds.
[0024]
In addition, as used herein, the term “bulky sulfoxidation products” refers to a combination of sulfoxides and sulfones having more than 12 carbon atoms, thiophenes with more than 4 carbon atoms, and sulfoxidation products of polyaromatic organosulfur compounds such as benzothiophenes, napthothiophenes, dibenzothiophenes, naptho-benzo-thiophene and alkyl and dialkyl derivatives of any of the aforementioned aromatic organosulfur compounds.
[0025]
Further, as used herein, “non-bulky sulfoxide products” refers to non-aromatic compounds including dimethyl sulfoxide, dibutyl sulfoxide and other sulfoxides having up to about 12 carbon atoms, or sulfoxides having a single ring structure, including thiophene sulfoxide and alkyl and dialkyl derivatives of thiophene sulfoxide with alkyl groups, having 1 to 4 carbon atoms.
[0026]
Still further, as used herein, “non-bulky sulfoxidation products” refers to non-aromatic compounds including dimethyl sulfoxide, dimethyl sulfone, dibutyl sulfoxide, dibutyl sulfone and other sulfoxides and sulfones having up to about 12 carbon atoms, or sulfoxides having a single ring structure, including thiophene sulfoxide, thiophene sulfone and alkyl and dialkyl derivatives of thiophene sulfoxide and thiophene sulfone with alkyl groups, having 1 to 4 carbon atoms.
source: https://patents.google.com/patent/US20130075305A1/en?q=dibenzothiophene&oq=dibenzothiophene
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A method of utilizing dibenzothiophenes in zeolite molecular sieve support type composite catalyst catalysis oxidation removal oil product
Application filed by 广东石油化工学院
2019-05-30
TIP: For those of us who cannot read Chinese characters, there is an easy way to learn who filed this patent. Copy the Chinese characters and paste them into Google®. In this case, the result is Guangdong University of Petrochemical Technology (West Gate).
Abstract
The invention discloses a kind of methods using dibenzothiophenes in zeolite molecular sieve support type composite catalyst catalysis oxidation removal oil product, method includes the following steps: zeolite molecular sieve support type composite catalyst is mixed with the oil product containing dibenzothiophenes, oxidant is added and carries out catalytic oxidation, complete the removal to dibenzothiophenes in oil product, wherein zeolite molecular sieve support type composite catalyst is using zeolite molecular sieve as carrier, and load has molybdenum trioxide and titanium dioxide thereon.The method of the present invention has many advantages, such as that simple process, easy to operate, low in cost, removal efficiency is high, removal effect is good, it being capable of effective conversion of the realization to dibenzothiophenes in oil product quickly and efficiently, reach ultra high efficiency and ultra-deep oxidation sweetening, there is fabulous economic benefit and application prospect.
CN110157466A
Claims (10)
Hide Dependent
1. a kind of method using dibenzothiophenes in zeolite molecular sieve support type composite catalyst catalysis oxidation removal oil product, It is characterized in that, comprising the following steps: mix zeolite molecular sieve support type composite catalyst and the oil product containing dibenzothiophenes It closes, oxidant is added and carries out catalytic oxidation, completes the removal to dibenzothiophenes in oil product；The zeolite molecular sieve Support type composite catalyst is using zeolite molecular sieve as carrier, and load has molybdenum trioxide and titanium dioxide on the zeolite molecular sieve Titanium.
2. the method according to claim 1, wherein in the zeolite molecular sieve support type composite catalyst molybdenum and The mass ratio of titanium is 1~4: 4~1；The gross mass of molybdenum and titanium is zeolite point in the zeolite molecular sieve support type composite catalyst The 20%~25% of son sieve；Institute's zeolite molecular sieve is MCM-22.
3. according to the method described in claim 2, it is characterized in that, the zeolite molecular sieve support type composite catalyst is by following Any one method is prepared；
Method one, comprising the following steps:
S1, zeolite molecular sieve is made to zeolite molecular sieve suspension；
S2, zeolite molecular sieve suspension, tetrabutyl titanate solution obtained in step S1 and Ammoniun Heptamolybdate Solution are mixed, is stirred It mixes, impregnates, be centrifuged, drying obtains precursor mixture；
S3, precursor mixture obtained in step S2 is roasted, obtains zeolite molecular sieve support type composite catalyst；
Method two, comprising the following steps:
(1) zeolite molecular sieve suspension is made in zeolite molecular sieve；
(2) zeolite molecular sieve suspension obtained in step (1) is mixed with polyvinylpyrrolidone, is stirred, obtain zeolite point Son sieve mixed liquor；
(3) zeolite molecular sieve mixed liquor obtained in step (2), tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution are mixed, is stirred It mixes, is centrifuged, drying obtains precursor mixture；
(4) precursor mixture obtained in step (3) is roasted, obtains zeolite molecular sieve support type composite catalyst.
4. according to the method described in claim 3, it is characterized in that, the preparation method of the zeolite molecular sieve suspension, including Following steps:
(a) zeolite molecular sieve is mixed with ammonium nitrate solution, is stirred, cleaned, drying repeats aforesaid operations 2~3 times；
(b) zeolite molecular sieve after drying in step (a) is roasted；
(c) zeolite molecular sieve after roasting in step (b) is mixed with water, ultrasound, stirring obtains zeolite molecular sieve suspension.
5. according to the method described in claim 4, it is characterized in that, in the step (a), the zeolite molecular sieve and ammonium nitrate The ratio of solution is 0.5g: 50mL；The concentration of the ammonium nitrate solution is 1mol/L；It is described stirring temperature be 80 DEG C at into Row；The time of the stirring is 2h；The drying carries out under vacuum conditions；The temperature of the drying is 80 DEG C；
In the step (b), the heating rate in the roasting process is 5 DEG C/min；It is described roasting temperature be 550 DEG C at into Row；The time of the roasting is 3h；
In the step (c), the ratio of zeolite molecular sieve and water after the roasting is 0.5g: 50mL；The time of the ultrasound For 30min.
6. according to the method described in claim 3, it is characterized in that, in the step S2, by tetrabutyl titanate solution and seven molybdenums Acid ammonium solution is added drop-wise in zeolite molecular sieve suspension simultaneously；The drop rate of the tetrabutyl titanate solution is 1.5mL/min ~2.5mL/min；The drop rate of the Ammoniun Heptamolybdate Solution is that the revolving speed of stirring described in 1.5mL/min~2.5mL/min is 1000r/min~2000r/min；The time of the stirring is 2h~4h；The time of the dipping is 20h~30h；The centrifugation Revolving speed be 5000r/min~6000r/min；
In the step S3, heating rate is 5 DEG C/min in the roasting process；The roasting carries out at being 550 DEG C in temperature； The time of the roasting is 3h.
7. according to the method described in claim 3, it is characterized in that, in the step (2), in the zeolite molecular sieve suspension Zeolite molecular sieve and polyvinylpyrrolidone mass ratio be 5: 3~5: 5；The revolving speed of the stirring be 1000r/min~ 2000r/min；The time of the stirring is 30min~60min；
In the step (3), tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution are added drop-wise in zeolite molecular sieve mixed liquor simultaneously； The drop rate of the tetrabutyl titanate solution is 1.5mL/min~2.5mL/min；The drop rate of the Ammoniun Heptamolybdate Solution For 1.5mL/min~2.5mL/min；The revolving speed of the stirring is 1000r/min~2000r/min；The time of the stirring is 2h~4h；The revolving speed of the centrifugation is 5000r/min~6000r/min；
In the step (4), heating rate is 5 DEG C/min in the roasting process；It is described roasting temperature be 550 DEG C at into Row；The time of the roasting is 3h.
8. method according to any one of claims 1 to 7, which is characterized in that the zeolite molecular sieve support type is compound The ratio of catalyst and the oil product containing dibenzothiophenes is 0.05g~0.20g: 20mL；The zeolite molecular sieve support type The ratio of composite catalyst and oxidant is 0.05g~0.20g: the 140 μ μ of L~560 L；The oxidant is cyclohexanone peroxide.
9. method according to any one of claims 1 to 7, which is characterized in that the catalytic oxidation is in temperature It is carried out at 80 DEG C~110 DEG C；The time of the catalytic oxidation is 15min~30min.
10. method according to any one of claims 1 to 7, which is characterized in that after the completion of the catalytic oxidation also The following steps are included: the catalyst after separation catalytic oxidation in obtained reaction mixture, aperture is used to have for 0.22 μm Machine filter film is filtered the reaction mixture obtained after separating catalyst.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of simple process, operation side Just, utilization zeolite molecular sieve support type composite catalyst catalysis oxidation low in cost, that removal efficiency is high, removal effect is good removes The method of dibenzothiophenes in oil product.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A method of dibenzothiophenes in oil product being removed using zeolite molecular sieve support type composite catalyst catalysis oxidation, The following steps are included: zeolite molecular sieve support type composite catalyst is mixed with the oil product containing dibenzothiophenes, oxygen is added Agent carries out catalytic oxidation, completes the removal to dibenzothiophenes in oil product；The zeolite molecular sieve support type is multiple Closing catalyst is using zeolite molecular sieve as carrier, and load has molybdenum trioxide and titanium dioxide on the zeolite molecular sieve.
Above-mentioned method, further improved, the quality of molybdenum and titanium in the zeolite molecular sieve support type composite catalyst Than being 1~4: 4~1；The gross mass of molybdenum and titanium is zeolite molecular sieve in the zeolite molecular sieve support type composite catalyst 20%~25%；Institute's zeolite molecular sieve is MCM-22.
Above-mentioned method, it is further improved, the zeolite molecular sieve support type composite catalyst by it is following any one Method is prepared；
Method one, comprising the following steps:
S1, zeolite molecular sieve is made to zeolite molecular sieve suspension；
S2, zeolite molecular sieve suspension, tetrabutyl titanate solution obtained in step S1 and Ammoniun Heptamolybdate Solution are mixed, Stirring impregnates, and is centrifuged, and drying obtains precursor mixture；
S3, precursor mixture obtained in step S2 is roasted, obtains zeolite molecular sieve support type composite catalyzing Agent；
Method two, comprising the following steps:
(1) zeolite molecular sieve suspension is made in zeolite molecular sieve；
(2) zeolite molecular sieve suspension obtained in step (1) is mixed with polyvinylpyrrolidone, stirs, is boiled Stone molecular sieve mixed liquor；
(3) zeolite molecular sieve mixed liquor obtained in step (2), tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution is mixed It closes, stirs, be centrifuged, drying obtains precursor mixture；
(4) precursor mixture obtained in step (3) is roasted, obtains zeolite molecular sieve support type composite catalyzing Agent.
Above-mentioned method, further improved, the preparation method of the zeolite molecular sieve suspension, comprising the following steps:
(a) zeolite molecular sieve is mixed with ammonium nitrate solution, is stirred, cleaned, drying repeats aforesaid operations 2~3 times；
(b) zeolite molecular sieve after drying in step (a) is roasted；
(c) zeolite molecular sieve after roasting in step (b) is mixed, ultrasound, stirring with water, obtains zeolite molecular sieve suspension Liquid.
Above-mentioned method, it is further improved, in the step (a), the ratio of the zeolite molecular sieve and ammonium nitrate solution Example is 0.5g: 50mL；The concentration of the ammonium nitrate solution is 1mol/L；The stirring carries out at being 80 DEG C in temperature；It is described to stir The time mixed is 2h；The drying carries out under vacuum conditions；The temperature of the drying is 80 DEG C；
In the step (b), the heating rate in the roasting process is 5 DEG C/min；The roasting is 550 DEG C in temperature Lower progress；The time of the roasting is 3h；
In the step (c), the ratio of zeolite molecular sieve and water after the roasting is 0.5g: 50mL；The ultrasound Time is 30min.
Above-mentioned method, it is further improved, it is in the step S2, tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution is same When be added drop-wise in zeolite molecular sieve suspension；The drop rate of the tetrabutyl titanate solution is 1.5mL/min~2.5mL/ min；The drop rate of the Ammoniun Heptamolybdate Solution is that the revolving speed of stirring described in 1.5mL/min~2.5mL/min is 1000r/min ~2000r/min；The time of the stirring is 2h~4h；The time of the dipping is 20h~30h；The revolving speed of the centrifugation is 5000r/min~6000r/min；
In the step S3, heating rate is 5 DEG C/min in the roasting process；The roasting is in the case where temperature is 550 DEG C It carries out；The time of the roasting is 3h.
Above-mentioned method, further improved, the zeolite point in the step (2), in the zeolite molecular sieve suspension The mass ratio of son sieve and polyvinylpyrrolidone is 5: 3~5: 5；The revolving speed of the stirring is 1000r/min~2000r/min； The time of the stirring is 30min~60min；
In the step (3), tetrabutyl titanate solution and Ammoniun Heptamolybdate Solution are added drop-wise to zeolite molecular sieve simultaneously and mixed In liquid；The drop rate of the tetrabutyl titanate solution is 1.5mL/min~2.5mL/min；The drop of the Ammoniun Heptamolybdate Solution Rate of acceleration is 1.5mL/min~2.5mL/min；The revolving speed of the stirring is 1000r/min~2000r/min；The stirring Time is 2h~4h；The revolving speed of the centrifugation is 5000r/min~6000r/min；
In the step (4), heating rate is 5 DEG C/min in the roasting process；The roasting is in the case where temperature is 550 DEG C It carries out；The time of the roasting is 3h.
Above-mentioned method, it is further improved, the zeolite molecular sieve support type composite catalyst with contain dibenzothiophenes Oil product ratio be 0.05g~0.20g: 20mL；The zeolite molecular sieve support type composite catalyst and oxidant Ratio is 0.05g~0.20g: 140 μ of μ L~560 L；The oxidant is cyclohexanone peroxide.
Above-mentioned method, further improved, the catalytic oxidation carries out at being 80 DEG C~110 DEG C in temperature；Institute The time for stating catalytic oxidation is 15min~30min.
Above-mentioned method, it is further improved, it is further comprising the steps of after the completion of the catalytic oxidation: separation catalysis The catalyst in reaction mixture obtained after oxidation reaction uses aperture to obtain for 0.22 μm of organic filter membrane to after separating catalyst To reaction mixture be filtered.
source: https://patents.google.com/patent/CN110157466A/en?q=dibenzothiophene&before=priority:20200427&after=priority:20180101&page=3
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Molecule-Based Equation Oriented Reactor Simulation System And Its Model Reduction
Inventors: Zhen Hou, Darin Campbell
Current Assignee: Aspen Technology Inc
Worldwide applications: 2019 WO US
Abstract
A computer-implemented method and system for modeling chemical reaction in a chemical reactor is disclosed. The method and system employ a molecule-based equation-oriented approach. Local-stored pre-estimated thermodynamic properties are generated based on a set of homologous series of compounds defined by the method and system. A set of reaction rate equations is automatically generated in equation-oriented format based on the defined set of homologous series of compounds, a system-defined set of permissible reactions, system-defined properties of the reactor compounds, and the locally-stored pre-estimated thermodynamic properties. The automatically generated set of reaction rate equations forms the model of chemical reactions in the chemical reactor.
US20190228843A1
Claims (40)
1. A computer-implemented method of modeling chemical reactions in a chemical reactor, the method comprising:
i) representing reactor compounds by defining a set of homologous series of compounds in the reactor, each homologous series within the set comprising a molecular type and a carbon number, the carbon number having an upper bound and a lower bound range;
ii) defining a set of permissible reactions for the defined set of homologous series of compounds;
iii) defining properties of the reactor compounds;
iv) generating and locally-storing pre-estimated thermodynamic properties based on the defined set of homologous series of compounds;
v) automatically coding a set of reaction rate equations in equation-oriented format based on the defined set of homologous series of compounds, the defined set of permissible reactions, the defined properties of the reactor compounds, and the generated and locally-stored pre-estimated thermodynamic properties,
the automatically coded set of reaction rate equations forming a model of chemical reactions in the chemical reactor.
2. The method of claim 1, wherein the molecular type of the homologous series includes any combination of one or more of: molecular hydrogen (H2); normal paraffin; pyrrole; benzene; pyridine; cyclohexane; thiophene; tetralin; benzothiophene; indole; naphthalene; quinolone; decalin; tetradecahydrophenanthrene; fluorene; tetrahydrophenanthrene; phenanthrene; benzoquinoline; octadecahydrochrysene; chrysene; naphthoquinoline; picene; naphthobenzothiophene (hard sulfur removal); naphthobenzothiophene (not as hard sulfur removal); dibenzothiophene (hard sulfur removal); dibenzothiophene (not as hard sulfur removal); carbazole; benzocarbazole; light molecule (
4. The method of claim 1, wherein the molecular type of the homologous series includes any combination of one or more of: naphthalene fused with naphthalene; naphthalene fused with benzothiophene; naphthalene fused with indole; naphthalene fused with quinoline; quinoline fused with quinoline; benzothiophene fused with quinoline; indole fused with quinoline; biphenyl fused with naphthalene; biphenyl fused with quinoline; benzothiophene fused with benzothiophene; benzothiophene fused with indole; biphenyl fused with benzothiophene; indole fused with indole; biphenyl fused with indole; phenanthrene fused with naphthalene; phenanthrene fused with quinoline; phenanthrene fused with benzothiophene; phenanthrene fused with indole; phenanthrene fused with phenanthrene; biphenyl fused with phenanthrene; benzoquinoline fused with quinoline; benzoquinoline fused with benzothiophene; benzoquinoline fused with indole; benzoquinoline fused with phenanthrene; benzoquinoline fused with benzoquinoline; biphenyl fused with benzoquinoline; dibenzothiophene (hard sulfur removal) fused with naphthalene; dibenzothiophene (hard sulfur removal) fused with quinoline; dibenzothiophene (hard sulfur removal) fused with benzothiophene; dibenzothiophene (hard sulfur removal) fused with indole; dibenzothiophene (hard sulfur removal) fused with phenanthrene; dibenzothiophene (hard sulfur removal) fused with benzoquinoline; dibenzothiophene (not hard sulfur removal) fused with naphthalene; dibenzothiophene (not hard sulfur removal) fused with benzoquinoline; dibenzothiophene (not hard sulfur removal) fused with benzothiophene; dibenzothiophene (not hard sulfur removal) fused with indole; dibenzothiophene (not hard sulfur removal) fused with phenanthrene; dibenzothiophene (not hard sulfur removal) fused with benzoquinoline; carbazole fused with naphthalene; carbazole fused with quinoline; carbazole fused with indole; carbazole fused with phenanthrene; carbazole fused with benzoquinoline; biphenyl fused with chrysene; biphenyl fused with naphthoquinoline; phenylnaphthalene fused with phenylnaphthalene; biphenyl fused with phenylnaphthalene; naphthobenzothiophene (hard sulfur removal) fused with phenylnaphthalene; chrysene fused with naphthalene; chrysene fused with quinoline; chrysene fused with benzothiophene; chrysene fused with indole; chrysene fused with phenanthrene; chrysene fused with benzoquinoline; chrysene fused with phenylnaphthalene; chrysene fused with benzothiophene1; chrysene fused with indole1; naphthoquinoline fused with quinoline; naphthoquinoline fused with benzothiophene; naphthoquinoline fused with indole; naphthoquinoline fused with benzoquinoline; naphthoquinoline fused with phenylnaphthalene; naphthoquinoline fused with benzothiophene1; naphthoquinoline fused with indole1; naphthobenzothiophene (hard sulfur removal) fused with benzothiophene; naphthobenzothiophene (hard sulfur removal) fused with indole; naphthobenzothiophene (hard sulfur removal) fused with naphthalene; naphthobenzothiophene (hard sulfur removal) fused with benzoquinoline; naphthobenzothiophene (hard sulfur removal) fused with biphenyl; naphthobenzothiophene (not hard sulfur removal) fused with benzothiophene; naphthobenzothiophene (not hard sulfur removal) fused with indole; naphthobenzothiophene (not hard sulfur removal) fused with naphthalene; naphthobenzothiophene (not hard sulfur removal) fused with benzoquinoline; naphthobenzothiophene (not hard sulfur removal) fused with phenylnaphthalene; benzocarbazole (not hard sulfur removal) fused with indole; benzocarbazole (not hard sulfur removal) fused with naphthalene; benzocarbazole (not hard sulfur removal) fused with quinoline; benzocarbazole (not hard sulfur removal) fused with phenylnaphthalene; picene fused with naphthalene; picene fused with quinoline; picene fused with biphenyl; naphthobenzothiophene (not hard sulfur removal) fused with biphenyl; picene fused with benzothiophene; picene fused with indole; picene fused with phenanthrene; picene fused with benzoquinoline; picene fused with phenylnaphthalene; picene fused with benzothiophene1; picene fused with indole1; picene fused with phenanthrene1; picene fused with benzoquinoline1; and picene fused with phenylnaphthalenel.
5. The method of claim 1, wherein the automatically coded set of reaction rate equations includes Langmuir-Hinshelwood-Hougen-Watson (LHHW) rate laws.
6. The method of claim 1, wherein generating and locally storing the pre-estimated thermodynamic properties comprises solving equations of kinetic rate and constraining kinetic rate constants by a linear free energy relationship (LFER).
7. The method of claim 1, wherein the automatically coded set of reaction rate equations comprises one or more of residuals, sparsity patterns, and analytical Jacobians in equation-oriented format.
8. The method of claim 1, wherein the defined properties of the reactor compounds include any combination of one or more of: molecular weight; total number of carbon atoms; total number of hydrogen atoms; total number of side chains; total number of aromatic rings; total number of naphthenic rings; total number of thiophenic rings; total number of pyrrolic rings; total number of pyridenic rings; total number of sulfur atoms; total number of nitrogen atoms; total number of oxygen atoms; total number of aromatic carbon atoms; total number of naphthenic carbon atoms; total number of paraffinic carbon atoms; total number of naphthenic six-carbon rings; total number of naphthenic five-carbon rings; boiling point; density; standard enthalpy of formation in gas phase; standard Gibbs free energy of formation in gas phase; a gas phase heat capacity coefficient; heat of vaporization; standard enthalpy of formation in liquid phase; a liquid phase heat capacity coefficient; a viscosity coefficient; and molecular type.
9. The method of claim 1, wherein the defined properties of reactor compounds include any combination of one or more of: total number of carbon atoms, total number of hydrogen atoms, total number of aromatic rings, total number of naphthenic rings, total number of thiophenic rings, total number of pyrrolic rings, total number of pyridenic rings, total number of sulfur atoms, total number of nitrogen atoms, total number of oxygen atoms, standard Gibbs free energy of formation, and standard enthalpy of formation.
10. The method of claim 1, wherein the defined properties of reactor compounds include any combination of one or more of total number of carbon atoms, total number of hydrogen atoms, standard Gibbs free energy of formation, and standard enthalpy of formation.
11. The method of claim 1, wherein the generated and locally-stored pre-estimated thermodynamic properties include any combination of one or more of: enthalpy of formation in gas phase at given temperature; Gibbs free energy of formation in gas phase at given temperature; gas phase heat capacity at given temperature; entropy in gas phase at given temperature; heat of vaporization; enthalpy of formation in liquid phase at given temperature; and liquid phase heat capacity at given temperature.
12. The method of claim 1, wherein the generated and locally-stored pre-estimated thermodynamic properties include any combination of one or more of: enthalpy of formation in gas phase at given temperature; Gibbs free energy of formation in gas phase at given temperature; gas phase heat capacity at given temperature; and entropy in gas phase at given temperature.
13. The method of claim 1, wherein the generated and locally-stored pre-estimated thermodynamic properties include any combination of one or more of enthalpy of formation in liquid phase at given temperature; and liquid phase heat capacity at given temperature.
14. The method of claim 1, wherein the defined set of permissible reactions includes any combination of one or more of: saturate a benzene ring in thiophenics with 3 H2; saturate a benzene ring in pyridinics or pyrrolics with 3 H2; saturate a benzene ring in pure hydrocarbon with 3 H2; saturate an isolated thiophenic ring with 2 H2; saturate a pyridinic ring fused with a benzene ring with 2 H2, or saturate an isolated pyrrolic ring with 2 H2; saturate a benzene ring in pure hydrocarbon with 2 H2; saturate a thiophenic ring fused with a benzene ring with 1 H2; saturate a pyrrolic ring fused with a benzene ring with 1 H2; naphthenics ring opening; paraffin hydrocracking; paraffin isomerization; desulfurization of dibenzothiophene structures; desulfurization of saturated thiophenics in saturated dibenzothiophene structures; desulfurization of saturated benzothiophene, or desulfurization of saturated thiophene structures; denitrogenation of saturated nitrogen rings in saturated carbazole structures; denitrogenation of saturated nitrogen rings in saturated indoles, pyrroles, pyridine, or quinine structures; dealkylation; and inter-core linkage cracking (ILCR).
15. The method of claim 1, wherein the defined set of permissible reactions includes paraffin isomerization.
16. The method of claim 1, wherein the defined set of permissible reactions includes aromatic ring condensation.
17. The method of claim 1, wherein the defined set of permissible reactions includes any combination of one or more of: aromatic paraffin hydrogenolysis; denitrogenation of saturated nitrogen rings in saturated indoles, pyrroles, pyridine, carbazole, or quinine structures; desulfurization of sulfides; desulfurization of thiophene structures; and aromatic ring condensation.
18. The method of claim 1, wherein automatically coding a set of reaction rate equations comprises parsing a reaction into reactants, products, and stoichiometric coefficients for the reactants and products.
19. The method of claim 1, wherein automatically coding a set of reaction rate equations comprises generating one or more of a residual, a sparsity, and an analytical Jacobian.
20. The method of claim 1, wherein generating the locally stored pre-estimated thermodynamic properties is by solving one or more equations of mass balance, energy balance, momentum balance, and kinetic rate and their associated ordinary differential equations.
21. The method of claim 20, wherein solving one or more equations of mass balance, energy balance, momentum balance, and kinetic rate and their associated ordinary differential equations further comprises providing initial solutions of the one or more equations.
22. The method of claim 1, further comprising outputting a table of results of the formed model to a flowsheet simulator.
23. The method of claim 1, wherein the formed model is a full reactor model, the method further comprising:
vi) creating a list of active species of the defined set of homologous series of compounds; and
vii) storing active species of the defined set of permissible reactions in the created list of active species, thereby creating a reduced reactor model from the full reactor model.
24. A computer system for modeling chemical reactions in a chemical reactor, the computer system comprising:
one or more processors operatively coupled to associated memory, the one or more processors configured to:
i) represent reactor compounds by defining a set of homologous series of compounds in the reactor, each homologous series within the set comprising a molecular type and a carbon number, the carbon number having an upper bound and a lower bound range;
ii) define a set of permissible reactions for the defined set of homologous series of compounds;
iii) define properties of the reactor compounds;
iv) generate and locally-store pre-estimated thermodynamic properties based on the defined set of homologous series of compounds;
v) automatically code a set of reaction rate equations in equation-oriented format based on the defined set of homologous series of compounds, the defined set of permissible reactions, the defined properties of the reactor compounds, and the generated and locally-stored pre-estimated thermodynamic properties,
the automatically coded set of reaction rate equations forming a model of chemical reactions in the chemical reactor.
25-27. (canceled)
28. The computer system of claim 24, wherein the automatically coded set of reaction rate equations include Langmuir-Hinshelwood-Hougen-Watson (LHHW) rate laws.
29. The computer system of claim 24, wherein the one or more processors generate and locally store the pre-estimated thermodynamic properties by solving equations of kinetic rate including constraining kinetic rate constants by a linear free energy relationship (LFER).
30. The computer system of claim 24, wherein the automatically coded set of reaction rate equations comprises one or more of residuals, sparsity patterns, and analytical Jacobians in equation-oriented format.
31. (canceled)
32. The computer system of claim 24, wherein the defined properties of reactor compounds include any combination of one or more of: total number of carbon atoms, total number of hydrogen atoms, total number of aromatic rings, total number of naphthenic rings, total number of thiophenic rings, total number of pyrrolic rings, total number of pyridenic rings, total number of sulfur atoms, total number of nitrogen atoms, total number of oxygen atoms, standard Gibbs free energy of formation, and standard enthalpy of formation.
33. (canceled)
34. The computer system of claim 24, wherein the generated and locally-stored pre-estimated thermodynamic properties include any combination of one or more of: enthalpy of formation in gas phase at given temperature; Gibbs free energy of formation in gas phase at given temperature; gas phase heat capacity at given temperature; entropy in gas phase at given temperature; heat of vaporization; enthalpy of formation in liquid phase at given temperature; and liquid phase heat capacity at given temperature.
35-40. (canceled)
41. The computer system of claim 24, wherein automatically coding a set of reaction rate equations comprises parsing a reaction into reactants, products, and stoichiometric coefficients for the reactants and products.
42. The computer system of claim 24, wherein automatically coding a set of reaction rate equations comprises generating one or more of a residual, a sparsity, and an analytical Jacobian.
43. The computer system of claim 24, wherein the one or more processors generate the locally stored pre-estimated thermodynamic properties by solving one or more equations of mass balance, energy balance, momentum balance, and kinetic rate and their associated ordinary differential equations.
44. The computer system of claim 43, wherein solving one or more equations of mass balance, energy balance, momentum balance, and kinetic rate and their associated ordinary differential equations by the processors further comprises providing initial solutions of the one or more equations.
45. The computer system of claim 24, further comprising one of the processors outputting a table of results of the formed model to a flowsheet simulator.
46. The computer system of claim 24, wherein the formed model is a full reactor model, the one or more processors further configured to:
vi) create a list of active species of the defined set of homologous series of compounds; and
vii) store active species of the defined set of permissible reactions in the created list of active species, thereby creating a reduced reactor model from the full reactor model.
47. A computer program product comprising:
a computer readable medium carrying instructions that model chemical reactions in a chemical reactor;
the instructions include computer code which when executed by a digital processor cause a simulator of the chemical reactor to:
i) represent reactor compounds by defining a set of homologous series of compounds in the reactor, each homologous series within the set comprising a molecular type and a carbon number, the carbon number having an upper bound and a lower bound range;
ii) define a set of permissible reactions for the defined set of homologous series of compounds;
iii) define properties of the reactor compounds;
iv) generate and locally-storing pre-estimated thermodynamic properties based on the defined set of homologous series of compounds;
v) automatically code a set of reaction rate equations in equation-oriented format based on the defined set of homologous series of compounds, the defined set of permissible reactions, the defined properties of the reactor compounds, and the generated and locally-stored pre-estimated thermodynamic properties,
the automatically coded set of reaction rate equations forming a model of chemical reactions in the chemical reactor.
SUMMARY
[0005]
Described herein is a computer-implemented method of modeling chemical reactions in a chemical reactor. Reactor compounds are represented by defining a set of homologous series of compounds in the reactor, each homologous series within the set comprising a molecular type and a carbon number range. A set of permissible reactions is defined for the defined set of homologous series of compounds. Properties of the reactor compounds are defined. Pre-estimated thermodynamic properties are generated and locally-stored. The pre-estimated thermodynamic properties are based on the defined set of homologous series of compounds. A set of reaction rate equations is automatically coded in equation oriented format based on: i) the defined set of homologous series of compounds; ii) the defined set of permissible reactions; iii) the defined properties of the reactor compounds; and iv) the generated and locally-stored pre-estimated thermodynamic properties. As a result, a model of chemical reactions in the chemical reactor is formed by the automatically coded set of reaction rate equations.
[0006]
Described herein is a computer system for modeling chemical reactions in a chemical reactor. The computer system can include one or more processors operatively coupled to associated memory. The processors are configured to represent reactor compounds by defining a set of homologous series of compounds in the reactor, each homologous series within the set comprising a molecular type and a carbon number range. The processors define a set of permissible reactions for the defined set of homologous series of compounds. The processors are configured to define properties of the reactor compounds. The processors are configured to generate and locally-store pre-estimated thermodynamic properties based on the defined set of homologous series of compounds. The processors are programmed so as to automatically code a set of reaction rate equations in equation oriented format based on: i) the defined set of homologous series of compounds; ii) the defined set of permissible reactions; iii) the defined properties of the reactor compounds; and iv) the generated and locally-stored pre-estimated thermodynamic properties. As a result, a model of chemical reactions in the chemical reactor is formed by the automatically coded set of reaction rate equations.
[0007]
Described herein is a computer program product that includes a computer readable medium carrying instructions that model chemical reactions in a chemical reactor. The instructions include computer code which when executed by a digital processor cause a simulator of the chemical reactor to implement the methods described herein.
[0008]
In embodiments, the molecular type of the homologous series can be one or more of: molecular hydrogen (H2); normal paraffin; pyrrole; benzene; pyridine; cyclohexane; thiophene; tetralin; benzothiophene; indole; naphthalene; quinolone; decalin; tetradecahydrophenanthrene; fluorene; tetrahydrophenanthrene; phenanthrene; benzoquinoline; octadecahydrochrysene; chrysene; naphthoquinoline; picene; naphthobenzothiophene (hard sulfur removal); naphthobenzothiophene (not as hard sulfur removal); dibenzothiophene (hard sulfur removal); dibenzothiophene (not as hard sulfur removal); carbazole; benzocarbazole; light molecule (
In some embodiments, the molecular type of the homologous series includes any combination of one or more of: naphthalene fused with naphthalene; naphthalene fused with benzothiophene; naphthalene fused with indole; naphthalene fused with quinoline; quinoline fused with quinoline; benzothiophene fused with quinoline; indole fused with quinoline; biphenyl fused with naphthalene; biphenyl fused with quinoline; benzothiophene fused with benzothiophene; benzothiophene fused with indole; biphenyl fused with benzothiophene; indole fused with indole; biphenyl fused with indole; phenanthrene fused with naphthalene; phenanthrene fused with quinoline; phenanthrene fused with benzothiophene; phenanthrene fused with indole; phenanthrene fused with phenanthrene; biphenyl fused with phenanthrene; benzoquinoline fused with quinoline; benzoquinoline fused with benzothiophene; benzoquinoline fused with indole; benzoquinoline fused with phenanthrene; benzoquinoline fused with benzoquinoline; biphenyl fused with benzoquinoline; dibenzothiophene (hard sulfur removal) fused with naphthalene; dibenzothiophene (hard sulfur removal) fused with quinoline; dibenzothiophene (hard sulfur removal) fused with benzothiophene; dibenzothiophene (hard sulfur removal) fused with indole; dibenzothiophene (hard sulfur removal) fused with phenanthrene; dibenzothiophene (hard sulfur removal) fused with benzoquinoline; dibenzothiophene (not hard sulfur removal) fused with naphthalene; dibenzothiophene (not hard sulfur removal) fused with benzoquinoline; dibenzothiophene (not hard sulfur removal) fused with benzothiophene; dibenzothiophene (not hard sulfur removal) fused with indole; dibenzothiophene (not hard sulfur removal) fused with phenanthrene; dibenzothiophene (not hard sulfur removal) fused with benzoquinoline; carbazole fused with naphthalene; carbazole fused with quinoline; carbazole fused with indole; carbazole fused with phenanthrene; carbazole fused with benzoquinoline; biphenyl fused with chrysene; biphenyl fused with naphthoquinoline; phenylnaphthalene fused with phenylnaphthalene; biphenyl fused with phenylnaphthalene; naphthobenzothiophene (hard sulfur removal) fused with phenylnaphthalene; chrysene fused with naphthalene; chrysene fused with quinoline; chrysene fused with benzothiophene; chrysene fused with indole; chrysene fused with phenanthrene; chrysene fused with benzoquinoline; chrysene fused with phenylnaphthalene; chrysene fused with benzothiophene1; chrysene fused with indole1; naphthoquinoline fused with quinoline; naphthoquinoline fused with benzothiophene; naphthoquinoline fused with indole; naphthoquinoline fused with benzoquinoline; naphthoquinoline fused with phenylnaphthalene; naphthoquinoline fused with benzothiophene1; naphthoquinoline fused with indole1; naphthobenzothiophene (hard sulfur removal) fused with benzothiophene; naphthobenzothiophene (hard sulfur removal) fused with indole; naphthobenzothiophene (hard sulfur removal) fused with naphthalene; naphthobenzothiophene (hard sulfur removal) fused with benzoquinoline; naphthobenzothiophene (hard sulfur removal) fused with biphenyl; naphthobenzothiophene (not hard sulfur removal) fused with benzothiophene; naphthobenzothiophene (not hard sulfur removal) fused with indole; naphthobenzothiophene (not hard sulfur removal) fused with naphthalene; naphthobenzothiophene (not hard sulfur removal) fused with benzoquinoline; naphthobenzothiophene (not hard sulfur removal) fused with phenylnaphthalene; benzocarbazole (not hard sulfur removal) fused with indole; benzocarbazole (not hard sulfur removal) fused with naphthalene; benzocarbazole (not hard sulfur removal) fused with quinoline; benzocarbazole (not hard sulfur removal) fused with phenylnaphthalene; picene fused with naphthalene; picene fused with quinoline; picene fused with biphenyl; naphthobenzothiophene (not hard sulfur removal) fused with biphenyl; picene fused with benzothiophene; picene fused with indole; picene fused with phenanthrene; picene fused with benzoquinoline; picene fused with phenylnaphthalene; picene fused with benzothiophene1; picene fused with indole1; picene fused with phenanthrene1; picene fused with benzoquinoline1; and picene fused with phenylnaphthalenel.
[0010]
In some embodiments, the automatically coded set of reaction rate equations include Langmuir-Hinshelwood-Hougen-Watson (LHHW) rate laws. In some embodiments, generating and locally storing the pre-estimated thermodynamic properties includes solving equations of kinetic rate and constraining kinetic rate constants by a linear free energy relationship (LFER). In some embodiments, the set of reaction rate equations comprises one or more of residuals, sparsity patterns, and analytical Jacobians in equation-oriented format.
[0011]
In some embodiments, the defined properties of the reactor compounds include one or more of: molecular weight; total number of carbon atoms; total number of hydrogen atoms; total number of side chains; total number of aromatic rings; total number of naphthenic rings; total number of thiophenic rings; total number of pyrrolic rings; total number of pyridenic rings; total number of sulfur atoms; total number of nitrogen atoms; total number of oxygen atoms; total number of aromatic carbon atoms; total number of naphthenic carbon atoms; total number of paraffinic carbon atoms; total number of naphthenic six-carbon rings; total number of naphthenic five-carbon rings; boiling point; density; standard enthalpy of formation in gas phase; standard Gibbs free energy of formation in gas phase; a gas phase heat capacity coefficient; heat of vaporization; standard enthalpy of formation in liquid phase; a liquid phase heat capacity coefficient; a viscosity coefficient; and molecular type. In one embodiment, the defined properties of reactor compounds are one or more of: total number of carbon atoms, total number of hydrogen atoms, total number of aromatic rings, total number of naphthenic rings, total number of thiophenic rings, total number of pyrrolic rings, total number of pyridenic rings, total number of sulfur atoms, total number of nitrogen atoms, total number of oxygen atoms, standard Gibbs free energy of formation, and standard enthalpy of formation. In another embodiment, the defined properties of reactor compounds are one or more of total number of carbon atoms, total number of hydrogen atoms, standard Gibbs free energy of formation, and standard enthalpy of formation.
[0012]
In some embodiments, the generated and locally-stored pre-estimated thermodynamic properties include one or more of: enthalpy of formation in gas phase at given temperature; Gibbs free energy of formation in gas phase at given temperature; gas phase heat capacity at given temperature; entropy in gas phase at given temperature; heat of vaporization; enthalpy of formation in liquid phase at given temperature; and liquid phase heat capacity at given temperature. In one embodiment, the generated and locally-stored pre-estimated thermodynamic properties are one or more of: enthalpy of formation in gas phase at given temperature; Gibbs free energy of formation in gas phase at given temperature; gas phase heat capacity at given temperature; and entropy in gas phase at given temperature. In other embodiments, the generated pre-estimated thermodynamic properties are enthalpy of formation in liquid phase at given temperature; and liquid phase heat capacity at given temperature.
[0013]
In some embodiments, the defined set of permissible reactions include one or more of: saturate a benzene ring in thiophenics with 3H2; saturate a benzene ring in pyridinics or pyrrolics with 3H2; saturate a benzene ring in pure hydrocarbon with 3H2; saturate an isolated thiophenic ring with 2H2; saturate a pyridinic ring fused with a benzene ring with 2H2, or saturate an isolated pyrrolic ring with 2H2; saturate a benzene ring in pure hydrocarbon with 2 H2; saturate a thiophenic ring fused with a benzene ring with 1H2; saturate a pyrrolic ring fused with a benzene ring with 1H2; naphthenics ring opening; paraffin hydrocracking; paraffin isomerization; desulfurization of thiophenics; desulfurization of saturated thiophenics in saturated dibenzothiophene structures; desulfurization of saturated benzothiophene, or desulfurization of saturated thiophene structures; denitrogenation of saturated nitrogen rings in saturated carbazole structures; denitrogenation of saturated nitrogen rings in saturated indoles, pyrroles, pyridine, or quinine structures; dealkylation; and inter-core linkage cracking (ILCR). In one embodiment, the defined set of permissible reactions is paraffin isomerization. In one embodiment, the defined set of permissible reactions includes aromatic ring condensation.
[0014]
In some embodiments, automatically coding a set of reaction rate equations comprises parsing a reaction into reactants, products, and stoichiometric coefficients for the reactants and products. In some embodiments, automatically coding a set of reaction rate equations includes generating one or more of a residual, a sparsity, and an analytical Jacobian.
[0015]
In some embodiments, generating the locally stored pre-estimated thermodynamic properties is by solving one or more equations of mass balance, energy balance, momentum balance, and kinetic rate and their associated ordinary differential equations. In some embodiments, solving one or more equations of mass balance, energy balance, momentum balance, and kinetic rate and their associated ordinary differential equations further includes providing initial solutions of the one or more equations.
[0016]
The method can also include outputting a table of results of the formed reactor model to a flowsheet simulator.
[0017]
In some embodiments, the formed reactor model is considered a full reactor model. The method can further include creating a list of active species of the defined set of homologous series of compounds, and storing active species of the defined set of permissible reactions in the created list of active species, thereby creating a reduced reactor model from the full reactor model. In system embodiments, the processor can be further configured to create a list of active species of the defined set of homologous series of compounds, and store active species of the defined set of permissible reactions in the created list of active species, thereby creating a reduced reactor model from the full reactor model.
[0018]
Any of the methods described herein can be implemented in computer systems, reactor simulation systems, refinery systems, and the like described herein.
[0019]
The methods described herein provide a number of benefits compared to prior methods. The methods can be used to create a molecular level kinetic model for refining chemistries in equation-oriented format. A large number of components and reactions is supported (e.g., on the order of 10000 species and 50000 reactions). Notably, the formed reactor model of embodiments can be described in terms of the molecular components. Thus, the formed model provides an improved level of detail, or resolution, that is useful for predicting properties, such as yield, octane number (e.g., research octane number (RON) for gasoline), and cetane number for diesel fuel. In some embodiments, improved detail can also be used to quantify particular compounds, such as quantity or mole percent of benzene. In some embodiments, improved detail can also be used to quantify particular atoms of interest, such as the amount of sulfur, which is typically expressed in parts-per-million (PPM). Other properties of interest can include viscosity, pour point, freeze point, and aromatic content.
[0020]
Prior methods required coding individual reaction rate equations, which is very time consuming and tedious. As a practical matter, coding individual reaction rate equations limits the number of equations that can be utilized due to the amount of time necessary to code the equations. Automatically coding a set of reaction rate equations by embodiments of the present invention greatly accelerates the development of a refining reactor model since it is often cost-prohibitive to manually code a large set of reaction rate equations.
[0021]
In embodiments where the method further includes creating a reduced reactor model, an additional advantage includes allowing users to simulate a large-scale molecule-based kinetic problem in terms of a molecule-based reduced model. In particular, the number of numerical variables is reduced to a smaller size, which further reduces memory and computational requirements (processing resources). Since there are fewer variables, the solution time of the reduced model for multiple beds is shorter while maintaining full molecular details for the reactor beds.
source: https://patents.google.com/patent/US20190228843A1/en?q=dibenzothiophene&before=priority:20200427&after=priority:20180101&page=3
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Metal nanoparticle-deposited, nitrogen-doped carbon adsorbents for removal of sulfur impurities in fuels
Inventors: Bi-Zeng Zhan, Zunqing He, Hoon Taek Chung, Piotr Zelenay
Current Assignees: Chevron USA Inc, Triad National Security LLC
Assigned to CHEVRON U.S.A. INC. 2019-03-07
Assigned to TRIAD NATIONAL SECURITY, LLC 2019-08-29
Abstract
Metal nanoparticle-deposited, nitrogen-doped carbon adsorbents are disclosed, along with methods of removing sulfur compounds from a hydrocarbon feed stream using these adsorbents.
US20190262798A1
Claims (20)
We claim:
1. A metal nanoparticle-deposited, nitrogen-doped carbon adsorbent, produced by a process comprising:
a) contacting at least one nitrogen precursor and a suitable first metal-containing salt in a first strong acid solution;
b) contacting a product of a) and an oxidant;
c) heating a product of b) in an inert atmosphere;
d) contacting a product of c) with a second strong acid solution;
e) heating a product of d) in an inert atmosphere, and
f) contacting the product of e) with a second metal-containing salt;
thereby producing the metal nanoparticle-deposited, nitrogen-doped carbon adsorbent.
2. The adsorbent of claim 1, wherein the second metal-containing salt is a gold-containing salt, and the metal nanoparticle-deposited, nitrogen-doped carbon adsorbent is a gold nanoparticle-deposited, nitrogen-doped carbon adsorbent.
3. The adsorbent of claim 1, wherein said a) is contacting two nitrogen precursors and the suitable first metal-containing salt in a first strong acid solution.
4. The adsorbent of claim 3, wherein said two nitrogen precursors are a first nitrogen precursor which is aniline and a second nitrogen precursor which is cyanimide.
5. The adsorbent of claim 1, wherein said b) is contacting the product of a) and (NH4)2S2O8, thus forming an oxidized product, and contacting said oxidized product with an aqueous solution containing carbon black and a low molecular weight alcohol.
6. The adsorbent of claim 1, wherein said c) is heating the product of b) to a first temperature of from about 35° C. to about 100° C., and then to a second temperature of from about 500° C. to about 1000° C.
7. The adsorbent of claim 1, wherein said d) is contacting the product of c) with either an H2SO4 solution or a HNO3 solution.
8. The adsorbent of claim 1, wherein said e) is heating the product of d) from about 500° C. to about 1000° C.
9. The absorbent of claim 1, wherein f) does not comprise a reducing agent.
10. The absorbent of claim 1, wherein f) comprises a reducing agent.
11. A method for removing sulfur compounds from a hydrocarbon feed stream comprising:
A) providing a first hydrocarbon feed stream, which is contaminated with the sulfur compounds; and
B) passing the first hydrocarbon feed stream through a desulfurization system comprising the metal nanoparticle-deposited, nitrogen-doped carbon adsorbent, to produce a second hydrocarbon feed stream which has about 30% to about 99.9% by weight less of the sulfur compounds than the first hydrocarbon feed stream, wherein the metal nano-particle-deposited, nitrogen-doped carbon absorbent is produced by a process comprising:
a) contacting at least one nitrogen precursor and a suitable first metal-containing salt in a first strong acid solution;
b) contacting a product of a) and an oxidant;
c) heating a product of b) in an inert atmosphere;
d) contacting a product of c) with a second strong acid solution;
e) heating a product of d) in an inert atmosphere, and
f) contacting the product of e) with a second metal-containing salt.
12. The method of claim 11, wherein the hydrocarbon feed stream is a liquid hydrocarbon feed stream.
13. The method of claim 12, wherein the liquid hydrocarbon feed stream is selected from the group consisting of diesel fuel, jet fuel, gasoline, kerosene, compressed natural gas, and liquefied petroleum gas (LPG).
14. The method of claim 11, wherein the sulfur compounds comprise dibenzothiophene (DBT).
15. The method of claim 11, wherein the sulfur compounds comprise 4,6-dimethyldibenzothiophene (DMDBT).
16. A method of making a metal nanoparticle-deposited, nitrogen-doped carbon adsorbent, the method comprising:
a) contacting at least one nitrogen precursor and a suitable first metal-containing salt in a first strong acid solution;
b) contacting a product of a) and an oxidant;
c) heating a product of b) in an inert atmosphere;
d) contacting a product of c) with a second strong acid solution;
e) heating a product of d) in an inert atmosphere, and
f) contacting the product of e) with a second metal-containing salt.
17. The method of claim 16, wherein the second metal-containing salt is a gold-containing salt, and the metal nanoparticle-deposited, nitrogen-doped carbon adsorbent is a gold nanoparticle-deposited, nitrogen-doped carbon adsorbent.
18. The method of claim 16, wherein said c) is heating the product of b) to a first temperature of from about 35° C. to about 100° C., and then to a second temperature of from about 500° C. to about 1000° C.
19. The method of claim 16, wherein said e) is heating the product of d) from about 500° C. to about 1000° C.
20. The method of claim 16, wherein f) does not comprise a reducing agent.
SUMMARY
[0008]
In one aspect, the invention relates to a method for removing sulfur compounds from a hydrocarbon feed stream, such as a liquid hydrocarbon feed stream. The method comprises the steps of: a) providing a first hydrocarbon feed stream, which is contaminated with sulfur compounds; and b) passing the first hydrocarbon feed stream through a desulfurization system comprising a metal nanoparticle-deposited, nitrogen-doped carbon adsorbent to produce a second hydrocarbon feed stream which has a substantially reduced concentration of sulfur compounds as compared to the first hydrocarbon feed stream. In some embodiments, the second hydrocarbon feed stream had a concentration of sulfur compounds in the second hydrocarbon feed stream which were from about 50% to about 99.9% less than the concentration of sulfur compounds in the first hydrocarbon feed stream. In some embodiments, the present invention provides a method for removing sulfur compounds from a hydrocarbon feed stream comprising: a) providing a first hydrocarbon feed stream, which is contaminated with sulfur compounds; and b) passing the first hydrocarbon feed stream through a desulfurization system comprising a metal nanoparticle-deposited, nitrogen-doped carbon adsorbent to produce a second hydrocarbon feed stream which has about 30% to about 99.9% by weight less sulfur compounds than the first hydrocarbon feed stream.
[0009]
In another aspect, the invention relates to a nitrogen-doped carbon adsorbent, produced by a process comprising: a) contacting at least one nitrogen precursor and a suitable first metal-containing salt in a first strong acid solution; b) contacting the product of a) and an oxidant; c) heating the product of b), thereby producing the nitrogen-doped carbon adsorbent.
[0010]
In yet another aspect, the present invention provides a metal nanoparticle-deposited, nitrogen-doped carbon adsorbent, produced by a process comprising: a) contacting at least one nitrogen precursor and a suitable first metal-containing salt in a first strong acid solution; b) contacting the product of a) and an oxidant; c) heating the product of b); d) contacting the product of c) with a second strong acid solution; e) heating the product of d); and f) contacting a nitrogen-doped carbon adsorbent with a second metal-containing salt; thereby producing the metal nanoparticle-deposited, nitrogen-doped carbon adsorbent.
[0011]
A general embodiment of the disclosure is a metal nanoparticle-deposited, nitrogen-doped carbon adsorbent, produced by a process comprising: a) contacting at least one nitrogen precursor and a suitable first metal-containing salt in a first strong acid solution; b) contacting a product of a) and an oxidant; c) heating a product of b) in an inert atmosphere; d) contacting a product of c) with a second strong acid solution; e) heating a product of d) in an inert atmosphere, f) contacting a nitrogen-doped carbon adsorbent with a second metal-containing salt; thereby producing the metal nanoparticle-deposited, nitrogen-doped carbon adsorbent. Another embodiment can be a method of making a metal nanoparticle-deposited, nitrogen-doped carbon absorbent. In some embodiments, the second metal-containing salt is a gold-containing salt, and the metal nanoparticle-deposited, nitrogen-doped carbon adsorbent is a gold nanoparticle-deposited, nitrogen-doped carbon adsorbent. In certain embodiments, said a) is contacting two nitrogen precursors and the suitable first metal-containing salt in a first strong acid solution. In a further embodiment, said two nitrogen precursors are a first nitrogen precursor which is aniline and a second nitrogen precursor which is cyanimide. In one embodiment, said b) is contacting the product of a) and (NH4)2S2O8, thus forming an oxidized product, and contacting said oxidized product with an aqueous solution containing carbon black and a low molecular weight alcohol. In some instances, said c) is heating the product of b) to a first temperature of from about 35° C. to about 100° C., and then to a second temperature of from about 500° C. to about 1000° C. In embodiments, said d) is contacting the product of c) with either an H2SO4 solution or a HNO3 solution. In certain embodiments, said e) is heating the product of d) from about 500° C. to about 1000° C. Further, f) can comprise a reducing agent, or f) may not comprise a reducing agent. In an embodiment, the second strong acid has a pH of less than 3, less than 2, less than 1, or less than 0.5. In an embodiment, the first strong acid has a pH of less than 3, less than 2, less than 1, or less than 0.5.
[0012]
Another general embodiment is a method for removing sulfur compounds from a hydrocarbon feed stream comprising: a) providing a first hydrocarbon feed stream, which is contaminated with the sulfur compounds; and b) passing the first hydrocarbon feed stream through a desulfurization system comprising the metal nanoparticle-deposited, nitrogen-doped carbon adsorbent of the disclosure, to produce a second hydrocarbon feed stream which has about 30% to about 99.9% by weight less of the sulfur compounds than the first hydrocarbon feed stream. The hydrocarbon feed stream can be a liquid hydrocarbon feed stream. In some embodiments, the liquid hydrocarbon feed stream is selected from the group consisting of diesel fuel, jet fuel, gasoline, kerosene, compressed natural gas, and liquefied petroleum gas (LPG). Further, the sulfur compounds can comprise dibenzothiophene (DBT) and/or 4,6-dimethyldibenzothiophene (DMDBT).
[0013]
The present invention may suitably comprise, consist of, or consist essentially of, the elements in the claims, as described herein.
source: https://patents.google.com/patent/US20190262798A1/en?q=dibenzothiophene&before=priority:20200427&after=priority:20180101&page=4
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Sulfur adsorbent and a method of separating sulfur compounds from a sulfur-containing mixture
Inventors: Khalid Al-Hooshani, Saheed A. Ganiyu,
Current Assignee: King Fahd University of Petroleum and Minerals
Application granted 2019-12-03
Abstract
A sulfur adsorbent comprising boric acid deposited on an activated carbon support, and a method of separating at least a portion of sulfur compounds from a sulfur-containing mixture with the sulfur adsorbent. Various combinations of embodiments of the sulfur adsorbent and the method are also provided.
US20190300798A1
Claims (20)
1. A method of separating at least a portion of one or more sulfur compounds from a sulfur-containing mixture, the method comprising:
contacting the sulfur-containing mixture with a sulfur adsorbent to form a treated mixture, wherein the sulfur adsorbent comprises boric acid deposited on an activated carbon support;
wherein the sulfur adsorbent has at least one of the following properties,
an average pore size of 1.0 to 10.0 nm,
a BET surface area of 200 to 1,000 m2/g,
a specific total pore volume of 0.3 to 1.0 cm3/g, or
a surface acidity of 0.8 to 1.8 mmol/g.
2. The method of claim 1, wherein a weight ratio of the boric acid to the activated carbon support is in the range of 1:500 to 1:5.
3. The method of claim 1, wherein a weight ratio of the boric acid to the activated carbon support is in the range of 1:120 to 1:50.
4. The method of claim 1, wherein the activated carbon support has a BET surface area of 400 to 1,200 m2/g.
5. The method of claim 1, wherein the boric acid is homogeneously deposited on the activated carbon support.
6. (canceled)
7. The method of claim 1, wherein an adsorption capacity of the sulfur adsorbent is up to 30.0 mg per gram of the sulfur adsorbent.
8. A method of separating at least a portion of one or more sulfur compounds from a sulfur-containing mixture, the method comprising:
contacting the sulfur-containing mixture with a sulfur adsorbent to form a treated mixture, wherein the sulfur adsorbent comprises boric acid deposited on an activated carbon support;
wherein the one or more sulfur compounds are selected from the group consisting of a sulfide, a disulfide, thiophene, an alkyl substituted thiophene, benzothiophene, an alkyl substituted benzothiophene, dibenzothiophene, and an alkyl substituted dibenzothiophene.
9. The method of claim 1, wherein a concentration of the one or more sulfur compounds in the sulfur-containing mixture ranges from 0.001% to 10% by weight relative to the total weight of the sulfur-containing mixture.
10. The method of claim 1,
wherein the treated mixture comprises the one or more sulfur compounds, and
wherein a ratio of a concentration of the one or more sulfur compounds in the treated mixture to the concentration of the one or more sulfur compounds in the sulfur-containing mixture is 1:2 to 1:1,000.
11. The method of claim 1, wherein the contacting is carried out at a temperature of 10° C. to 40° C.
12. The method of claim 1, wherein the sulfur-containing mixture is contacted with the sulfur adsorbent for at least 2 minutes, but no more than 6 hours.
13. The method of claim 1, further comprising:
regenerating the sulfur adsorbent.
14. The method of claim 13,
wherein the regenerating is carried out by treating the sulfur adsorbent with an organic solvent, and
wherein the organic solvent is at least one selected from the group consisting of acetone, methanol, toluene, benzene, and xylene.
15. The method of claim 13,
wherein the sulfur adsorbent is regenerated for up to ten times, and
wherein an adsorption capacity of the sulfur adsorbent is reduced by no more than 10%, relative to an initial adsorption capacity of the sulfur adsorbent.
16. The method of claim 1,
wherein the sulfur-containing mixture comprises one or more hydrocarbon compounds, and
wherein a selectivity of the sulfur adsorbent towards adsorbing the one or more sulfur compounds is at least 90% by mole.
17. A sulfur adsorbent, comprising boric acid deposited on an activated carbon support, wherein a weight ratio of the boric acid to the activated carbon support is in the range of 1:200 to 1:5;
wherein the sulfur adsorbent has at least one of the following properties,
an average pore size of 1.0 to 10.0 nm,
a BET surface area of 200 to 1,000 m2/g,
a specific total pore volume of 0.3 to 1.0 cm3/g, or
a surface acidity of 0.5 to 1.8 mmol/g.
18. The sulfur adsorbent of claim 17, wherein a weight ratio of the boric acid to the activated carbon support is in the range of 1:120 to 1:50.
19. The sulfur adsorbent of claim 17, wherein the boric acid is homogeneously deposited on the activated carbon support.
20. (canceled)
BRIEF SUMMARY OF THE INVENTION
[0010]
According to a first aspect, the present disclosure relates to a method of separating at least a portion of one or more sulfur compounds from a sulfur-containing mixture, the method involving contacting the sulfur-containing mixture with a sulfur adsorbent to form a treated mixture, wherein the sulfur adsorbent comprises boric acid deposited on an activated carbon support.
[0011]
In one embodiment, a weight ratio of the boric acid to the activated carbon support is in the range of 1:500 to 1:5.
[0012]
In one embodiment, a weight ratio of the boric acid to the activated carbon support is in the range of 1:120 to 1:50.
[0013]
In one embodiment, the activated carbon support has a BET surface area of 400 to 1,200 m2/g.
[0014]
In one embodiment, the boric acid is homogeneously deposited on the activated carbon support.
[0015]
In one embodiment, the sulfur adsorbent has at least one of the following properties, a) an average pore size of 1.0 to 10.0 nm, b) a BET surface area of 200 to 1,000 m2/g, c) a specific total pore volume of 0.3 to 1.0 cm3/g, or d) a surface acidity of 0.8 to 1.8 mmol/g.
[0016]
In one embodiment, an adsorption capacity of the sulfur adsorbent is up to 30.0 mg per gram of the sulfur adsorbent.
[0017]
In one embodiment, the one or more sulfur compounds are selected from the group consisting of a sulfide, a disulfide, thiophene, an alkyl substituted thiophene, benzothiophene, an alkyl substituted benzothiophene, dibenzothiophene, and an alkyl substituted dibenzothiophene.
[0018]
In one embodiment, a concentration of the one or more sulfur compounds in the sulfur-containing mixture ranges from 0.001% to 10% by weight relative to the total weight of the sulfur-containing mixture.
[0019]
In one embodiment, the treated mixture comprises the one or more sulfur compounds, wherein a ratio of a concentration of the one or more sulfur compounds in the treated mixture to the concentration of the one or more sulfur compounds in the sulfur-containing mixture is 1:2 to 1:1,000.
[0020]
In one embodiment, the contacting is carried out at a temperature of 10° C. to 40° C.
[0021]
In one embodiment, the sulfur-containing mixture is contacted with the sulfur adsorbent for at least 2 minutes, but no more than 6 hours.
[0022]
In one embodiment, the method further involves regenerating the sulfur adsorbent.
[0023]
In one embodiment, the regenerating is carried out by treating the sulfur adsorbent with an organic solvent, wherein the organic solvent is at least one selected from the group consisting of acetone, methanol, toluene, benzene, and xylene.
[0024]
In one embodiment, the sulfur adsorbent is regenerated for up to ten times, wherein an adsorption capacity of the sulfur adsorbent is reduced by no more than 10%, relative to an initial adsorption capacity of the sulfur adsorbent.
[0025]
In one embodiment, the sulfur-containing mixture comprises one or more hydrocarbon compounds, wherein a selectivity of the sulfur adsorbent towards adsorbing the one or more sulfur compounds is at least 90% by mole.
[0026]
According to a second aspect, the present disclosure relates to a sulfur adsorbent including boric acid deposited on an activated carbon support, wherein a weight ratio of the boric acid to the activated carbon support is in the range of 1:200 to 1:5.
[0027]
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.google.com/patent/US20190300798A1/en?q=(dibenzothiophene)&before=priority:20200427&after=priority:20180101&oq=(dibenzothiophene)+before:priority:20200427+after:priority:20180101&page=5
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Method for converting dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound
Application filed by
Chengdu Institute of Biology
2019-09-20
Abstract
The invention relates to the technical field of organic chemistry, in particular to a method for converting a dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound. The specific scheme is as follows: the invention takes a dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound as a raw material, and the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound is heated in polar or deuterated solution under alkaline conditions or is subjected to desulfurization reaction in the presence of a metal reagent, or is converted into a compound widely applied in the fields of organic chemistry and pharmaceutical chemistry. The method has the advantages of mild reaction conditions, high yield, good reaction universality, simple operation and the like.
CN110683940A
Claims (10)
1. A method for converting dibenzo [ c, e ] [1,2] oxathiane-6-oxide compounds, which comprises: the transformation method comprises the following steps:
adding dibenzo [ c, e ] [1,2] oxathiane-6-oxide compounds into a polar solvent or a deuterated solvent under an alkaline condition, and heating at 30-200 ℃ to react to obtain a desulfurization product;
or adding dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound into an organic metal reagent I, and after the reaction is finished, forming a ring-opened 2 '-sulfinyl- [1,1' -biphenyl ] -2-phenol compound;
or, adding dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound into alkaline solution and electrophilic reagent, and after the reaction is completed, forming ring-opened 2 '-sulfonyl- [1,1' -biphenyl ] -2-phenol compound or 2 '-sulfonyl- [1,1' -biphenyl ] -2-phenol ether compound;
or adding dibenzo [ c, e ] [1,2] oxathiane-6-oxide compounds into an organic solvent I, reducing by lithium aluminum hydride, and forming ring-opened 2 '-mercapto- [1,1' -biphenyl ] -2-phenolic compounds after the reaction is finished;
or adding a dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound into a hydrogen peroxide and glacial acetic acid solution, heating to 30-200 ℃, oxidizing to form dibenzo [ c, e ] [1,2] oxathiane-6, 6-dioxide, adding the product into an organic metal reagent II, and forming a ring-opened 2 '-sulfonyl- [1,1' -biphenyl ] -2-phenol or 2 '-hydroxy- [1,1' -biphenyl ] -2-sulfonate or 2 '-hydroxy- [1,1' -biphenyl ] -2-sulfonamide compound;
or adding dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound into an aqueous solution containing an organic solvent II, heating with phosphate buffer solution or treating with NaOH to form ring-opened 2 '-hydroxy- [1,1' -biphenyl ] -2-sulfinate.
2. The method of claim 1, wherein the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound is obtained by the following steps: the structural general formula of the dibenzo [ c, e ] [1,2] oxathiane-6-oxide is as follows:
wherein R is1，R2Respectively one of alkyl, alkoxy, amino, aryl, alkenyl, alkynyl and acyl.
3. A dibenzo [ c, e ] according to claim 1][1,2]The transformation method of the oxathiane-6-oxide compound is characterized in that: the alkaline condition is one of potassium carbonate, potassium tert-butoxide and cesium carbonate, the polar solvent is one of N, N-dimethylformamide, acetonitrile and tetrahydrofuran, and the deuterated solvent contains 10% of D2C of OD3CN、CDCl3、CD3OD、D2O、DMF-D7、Toluene-D6、Pyridine-D5、DMSO-D6One kind of (1).
4. The method of claim 1, wherein the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound is obtained by the following steps: the organic metal reagent I is one of an organic magnesium reagent, an organic lithium reagent and an organic zinc reagent.
5. The method of claim 1, wherein the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound is obtained by the following steps: the alkaline solution is NaOH, and the electrophilic reagent is halogenated alkane.
6. The method of claim 1, wherein the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound is obtained by the following steps: the organic solvent I is diethyl ether or THF.
7. The method of claim 1, wherein the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound is obtained by the following steps: the organic metal reagent II is one of an alkyl lithium reagent, an alkoxy sodium reagent, an amino lithium reagent and a phenyl lithium reagent.
8. The method of claim 1, wherein the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound is obtained by the following steps: the organic solvent II is one of THF, DMF and acetonitrile.
9. The method of claim 1, wherein the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound is obtained by the following steps:
when the molar ratio of the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound to the alkaline solution to the electrophilic reagent is 1:1.2:1.2, synthesizing a 2 '-sulfonyl- [1,1' -biphenyl ] -2-phenol compound;
when the molar ratio of the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound to the alkaline solution to the electrophilic reagent is 1:3: 3-4, synthesizing the 2 '-sulfonyl- [1,1' -biphenyl ] -2-phenol ether compound.
10. The method of claim 1, wherein the dibenzo [ c, e ] [1,2] oxathiane-6-oxide compound is obtained by the following steps: the desulfurization product is a [1,1' -biphenyl ] -2-phenol compound or a poly-deuterated- [1,1' -biphenyl ] -2-phenol compound, wherein the [1,1' -biphenyl ] -2-phenol compound is activated by a hydroxyl-oriented C-H bond under the action of a transition metal catalyst to obtain a poly-substituted biphenyl phenol compound; the transition metal catalyst is palladium acetate.
BRIEF SUMMARY OF THE INVENTION
[0010]
According to a first aspect, the present disclosure relates to a method of separating at least a portion of one or more sulfur compounds from a sulfur-containing mixture, the method involving contacting the sulfur-containing mixture with a sulfur adsorbent to form a treated mixture, wherein the sulfur adsorbent comprises boric acid deposited on an activated carbon support.
[0011]
In one embodiment, a weight ratio of the boric acid to the activated carbon support is in the range of 1:500 to 1:5.
[0012]
In one embodiment, a weight ratio of the boric acid to the activated carbon support is in the range of 1:120 to 1:50.
[0013]
In one embodiment, the activated carbon support has a BET surface area of 400 to 1,200 m2/g.
[0014]
In one embodiment, the boric acid is homogeneously deposited on the activated carbon support.
[0015]
In one embodiment, the sulfur adsorbent has at least one of the following properties, a) an average pore size of 1.0 to 10.0 nm, b) a BET surface area of 200 to 1,000 m2/g, c) a specific total pore volume of 0.3 to 1.0 cm3/g, or d) a surface acidity of 0.8 to 1.8 mmol/g.
[0016]
In one embodiment, an adsorption capacity of the sulfur adsorbent is up to 30.0 mg per gram of the sulfur adsorbent.
[0017]
In one embodiment, the one or more sulfur compounds are selected from the group consisting of a sulfide, a disulfide, thiophene, an alkyl substituted thiophene, benzothiophene, an alkyl substituted benzothiophene, dibenzothiophene, and an alkyl substituted dibenzothiophene.
[0018]
In one embodiment, a concentration of the one or more sulfur compounds in the sulfur-containing mixture ranges from 0.001% to 10% by weight relative to the total weight of the sulfur-containing mixture.
[0019]
In one embodiment, the treated mixture comprises the one or more sulfur compounds, wherein a ratio of a concentration of the one or more sulfur compounds in the treated mixture to the concentration of the one or more sulfur compounds in the sulfur-containing mixture is 1:2 to 1:1,000.
[0020]
In one embodiment, the contacting is carried out at a temperature of 10° C. to 40° C.
[0021]
In one embodiment, the sulfur-containing mixture is contacted with the sulfur adsorbent for at least 2 minutes, but no more than 6 hours.
[0022]
In one embodiment, the method further involves regenerating the sulfur adsorbent.
[0023]
In one embodiment, the regenerating is carried out by treating the sulfur adsorbent with an organic solvent, wherein the organic solvent is at least one selected from the group consisting of acetone, methanol, toluene, benzene, and xylene.
[0024]
In one embodiment, the sulfur adsorbent is regenerated for up to ten times, wherein an adsorption capacity of the sulfur adsorbent is reduced by no more than 10%, relative to an initial adsorption capacity of the sulfur adsorbent.
[0025]
In one embodiment, the sulfur-containing mixture comprises one or more hydrocarbon compounds, wherein a selectivity of the sulfur adsorbent towards adsorbing the one or more sulfur compounds is at least 90% by mole.
[0026]
According to a second aspect, the present disclosure relates to a sulfur adsorbent including boric acid deposited on an activated carbon support, wherein a weight ratio of the boric acid to the activated carbon support is in the range of 1:200 to 1:5.
[0027]
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.google.com/patent/CN110683940A/en?q=(dibenzothiophene)&before=priority:20200427&after=priority:20180101&oq=(dibenzothiophene)+before:priority:20200427+after:priority:20180101&page=7
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Method for oxidation of sulfur-containing compounds
Inventor: Robert William McGaff
Application filed by Mcgaff Robert William 2020-02-27
Abstract
Various embodiments disclosed relate to a method of oxidizing sulfur-containing compounds. The method involves contacting a sulfur-containing compound with a helmet phthalocyaninato-type catalyst in the presence of an oxidant. The present invention also provides a method of removing undesired sulfur-containing compounds from a fluid, such as natural gas, crude oil or an aqueous waste stream.
WO2020041284A1
Claims
CLAIMS What is claimed is:
1. A method of oxidizing a sulfur-containing compound, comprising:
contacting the sulfur-containing compound with a catalyst in the presence of an oxidant, the catalyst having the structure:
Figure imgf000051_0001
wherein
M is a metal,
axial ligand L is a solvent molecule or absent,
at each occurrence, RA and RB are independently chosen from -H, halide, an organic group, and a hydrophilic group, or RA and RB together form a fused aromatic ring with the ring upon which RA and RB are substituted, RA and RB together having the structure:
Figure imgf000051_0002
at each occurrence, R1, R2, R3, R4, R5, and R6 are each independently chosen from -H, halide, an organic group, a hydrophilic group, a salt thereof, a substituted or unsubstituted (Ci-C5o)hydrocarbyl ester thereof, and a combination thereof.
2. The method of claim 1, wherein the only oxidant present in stoichiometric or greater quantities is molecular oxygen of ambient air.
3. The method of claim 1, wherein the catalyst has the structure:
Figure imgf000052_0001
wherein
M is a metal,
L is a solvent molecule or absent, and
at each occurrence, R1, R2, R3, R4, R5, and R6 are independently chosen from - H, halide, an organic group, and a hydrophilic group.
4. The method of claim 1, wherein at each occurrence, the hydrophilic group is independently chosen from -C(0)0H, -0-C(0)0H, -R(0)(0H)2, -0P(0)(0H)2, -S(0)(0)0H, -0S(0)(0)0H, a salt thereof, a substituted or unsubstituted (Ci-C5o)hydrocarbyl ester thereof, and a combination thereof.
5. The method of claim 1, wherein the catalyst has the structure:
Figure imgf000053_0001
wherein axial ligand L is H2O.
6. The method of claim 1, wherein the catalyst has the structure:
Figure imgf000054_0001
7. The method of claim 1, wherein the contacting is performed at room temperature.
8. The method of claim 1, wherein the sulfur-containing compound is in solution.
9. The method of claim 1, wherein the sulfur-containing compound is in the vapor phase.
10. The method of claim 1, wherein the sulfur-containing compound is in a crude oil, a refined oil, a natural gas, an aqueous waste stream, an exhaust gas waste stream, a combustion gas waste stream, or a mixture thereof.
11. The method of claim 1, wherein the solvent comprises water, C1-C10 alcohol, non polar organic solvent, or a combination thereof.
12. The method of claim 1, wherein the sulfur-containing compound has the structure
O
X-S-H X-S-Y nr X-&-Y
wherein each of X and Y is independently C1-C20 alkyl, C6-C10 aryl or C2-C10 heteroaryl, each of which may be optionally substituted, and X and Y may be linked so as to form a ring.
13. The method of claim 1, wherein the sulfur-containing compound is an aromatic thiol, a non-aromatic thiol or a thioether.
14. The method of claim 1, wherein the sulfur-containing compound is a substituted or unsubstituted alkylthiol.
15. The method of claim 1, wherein the sulfur-containing compound is
Figure imgf000055_0001
wherein n is 0-10 and m is 0-10.
16. A method of removing sulfur-containing compounds from a fluid, comprising:
contacting the fluid and sulfur-containing compounds with a catalyst in the presence of an oxidant to produce an oxidized sulfur-containing compound; and then
separating the oxidized sulfur-containing compound from the fluid, wherein
the catalyst has the structure
Figure imgf000056_0001
wherein
M is a metal,
axial ligand L is a solvent molecule or absent,
at each occurrence, RA and RB are independently chosen from -H, halide, an organic group, and a hydrophilic group, or RA and RB together form a fused aromatic ring with the ring upon which RA and RB are substituted, RA and RB together having the structure:
Figure imgf000056_0002
at each occurrence, R1, R2, R3, R4, R5, and R6 are each independently chosen from -H, halide, an organic group, a hydrophilic group, a salt thereof, a substituted or unsubstituted (Ci-Cso)hydrocarbyl ester thereof, and a combination thereof.
17. The method of claim 16, wherein the fluid is a crude oil, a refined oil, a hydrocarbon mixture, a fossil fuel, a natural gas, petroleum, coal, an aqueous waste stream, an exhaust gas waste stream, a combustion gas waste stream, a combusted crude oil, a combusted refined oil, a combusted hydrocarbon mixture, a combusted fossil fuel, a combusted natural gas, combusted petroleum, combusted coal, or a mixture thereof.
18. The method of claim 16, wherein the fluid is a liquid, a gas, or a mixture thereof.
19. The method of claim 16, wherein the contacting step is performed at room temperature.
20. The method of claim 16, wherein the oxidant is molecular oxygen in ambient air and no other oxidant is present in stoichiometric or greater quantities.
SUMMARY OF THE INVENTION
[0003] The present invention provides a method of oxidizing a sulfur-containing compound. In various embodiments, the method includes contacting the sulfur-containing compound with a helmet phthalocyaninato-type catalyst in the presence of an oxidant.
[0004] The present invention also provides a method of removing sulfur-containing compounds from a fluid. The method involves contacting the fluid with a helmet
phthalocyaninato-type catalyst in the presence of an oxidant to produce an oxidized sulfur- containing compound; and then separating the oxidized sulfur-containing compound from the fluid.
[0005] In various embodiments, the methods of the present invention involve use of a helmet phthalocyaninato-type catalyst having the structure:
Figure imgf000003_0001
wherein
M is a metal,
axial ligand L is a solvent molecule or absent,
at each occurrence, RA and RB are independently chosen from -H, halide, an organic group, and a hydrophilic group, or RA and RB together form a fused aromatic ring with the ring upon which RA and RB are substituted, RA and RB together having the structure:
Figure imgf000003_0002
at each occurrence, R1, R2, R3, R4, R5, and R6 are each independently chosen from -H, halide, an organic group, a hydrophilic group, a salt thereof, a substituted or unsubstituted (Ci-C5o)hydrocarbyl ester thereof, and a combination thereof.
[0006] Advantages, some of which are unexpected, are achieved by various embodiments of the present disclosure. In various embodiments, the present invention provides an efficient, economical, environmentally-friendly method of oxidizing sulfur- containing compounds. For example, various embodiments of the present invention can be performed at room temperature, thus providing the environmental and economic benefit of reducing energy consumption. As another example, various embodiments of the present invention can be performed without use of solvent or by use of environmentally-friendly solvents, e.g., water and alcohol. As another example, various embodiments of the present invention can be performed without the use of undesirable metals such as toxic heavy metals or expensive precious metals, thus resulting in a safer and more economic process.
source: https://patents.google.com/patent/WO2020041284A1/en?q=(dibenzothiophene)&before=priority:20200427&after=priority:20180101&oq=(dibenzothiophene)+before:priority:20200427+after:priority:20180101&page=12
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Starting Down the Startup Path: TOC – Table of Contents
If you enjoyed this post, you might like some of the others in this series. Here is a convenient way to find them.
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Starting Down the Startup Path (Part 1 of a series)
How do you find emerging technology? One way is to focus on startups.
OK, fine, but how do you discover the startups that offer a technology of interest to you? One way is to focus on venture capital firms that focus on the areas of interest to you.
Read full post at:
https://desulf.blogspot.com/2019/12/starting-down-startup-path-part-1-of.html
Starting Down the Startup Path (Part 2 of a series)
Anyone involved in venture capital or its variants is interested in identifying potential candidates for investment opportunity. Finding these candidates is not easy. But a place to start on startups is to see what companies other venture capital firms have identified.
Read full post at:
https://desulf.blogspot.com/2019/12/starting-down-startup-path-part-2-of.html
Starting Down the Startup Path (Part 3 of a series)
Panning for Google® gold: startups with promising new technologies
The previous post in this series featured the List of Top Oil and Gas Private Equity Firms discovered as the result of a Google® search. The list focuses on companies pursuing acquisition and development of existing resources. While the list will be useful to many, this series of posts focuses on techniques you can use to identify startups with promising new technologies.
So, on to the next step in the quest to find new technology on the cusp of successful deployment.
Read full post at:
https://desulf.blogspot.com/2020/01/starting-down-startup-path-part-3-of.html
Starting Down the Startup Path (Part 4 of a series)
Nothing Ventured, Nothing Gained: Follow the Lead of the Oil Majors
How do you identify startups that fit your corporate goals? One way is to set up and advertise a venture capital unit, which enables young companies to pitch their technology to your corporation.
And that is just what several oil majors have done.
Studying their portfolios can provide a wealth of helpful information, whether you are a venture capitalist, a startup, or simply interested in identifying emerging technology.
Read full post at:
https://desulf.blogspot.com/2020/01/starting-down-startup-path-part-4-of.html
Starting Down the Startup Path (Part 5 of a series): Searching Patents
Patents: Emerging Tech
Patents are a rich source of cutting-edge research. And much of the research reported in patents never appears in peer reviewed journals. So, to identify emerging technology in your field, consider searching the patent literature on a regular basis.
TIP: Read Tips for reading patents: a concise introduction for scientists for an excellent overview on this topic.
Read full post at:
https://desulf.blogspot.com/2020/02/start-up-startdown-path-parti-5-of.html
Starting Down the Startup Path (Part 6 of a series): Reviewing Patents
Searching for patents is iterative. You type in some keywords. Results reveal more keywords. You type in those keywords. And repeat.
This can be really tedious, irksome even. Sometimes it is hard to figure out whether a given patent is even relevant to your needs.
Fortunately, a number of experts have offered tips to make it easier to read a patent quickly.
TIP: Google® how to read a patent for more tips on efficient ways to review a patent
Read full post at:
https://desulf.blogspot.com/2020/03/starting-down-startup-path-part-6-of.html
Starting Down the Startup Path (Part 7 of a series): Patents and Run On Sentences
Per USPO rules, the Claims in a patent must be stated in a single sentence. In many cases, the “single sentence” can be, thanks to colons, commas, semicolons, et al., several hundred words long.
But remember that, as difficult as it may be to wrap your head around any given claim, it still is faster than reading the whole patent.
Read full post at:
https://desulf.blogspot.com/2020/03/starting-down-startup-path-part-7-of.html
Starting Down the Startup Path (Part 8 of a series): Mining Patents for Keywords
Mining patents for useful information can be tedious. One thing you can do is to look for keywords to use in Google® searches. For example, in a previous post I listed a Breakthrough Technologies LLC patent with the following claim …
Read full post at:
https://desulf.blogspot.com/2020/03/starting-down-startup-path-part-8-of.html
Starting Down the Startup Path (Part 9 of a series): PTQ Catalysis 2020
PTQ Catalysis 2020 is ready to view at www.eptq.com. As always, it is rich in useful information. In the context of our Startdown the Startup Path series of posts, one article in particular caught my eye …
Pilot plant studies of hydrotreating catalysts
Read full post at:
https://desulf.blogspot.com/2020/03/starting-down-startup-path-part-9-of.html
Starting Down the Startup Path (Part 10 of a series): The Bigness of Machine Learning
Big data is a big deal. We humans generate so much data that our puny brains are unable to process it. So we have created machines to do that for us.
There is a whole discipline called machine learning designed to train these machines to process massive amounts of data in useful ways.
“Machine learning,” as Serdar Yegulalp notes in an InfoWorld article, “is a complex discipline. But implementing machine learning models is far less daunting and difficult than it used to be, thanks to machine learning frameworks—such as Google’s TensorFlow—that ease the process of acquiring data, training models, serving predictions, and refining future results.”
Read full post at:
https://desulf.blogspot.com/2020/03/starting-down-startup-path-part-10-of.html
Starting Down the Startup Path (Part 11 of a series): Thread the Needle
In a horse race, the goal is to bet on the winning horse. Common sense tells us that if we knew for a certainty which horse would win the race, racing them would be pointless. The same logic applies to new technologies, and the companies that create them.
That’s why it can be useful to look at companies that have been examined by investment funds like the Columbia Seligman Communications and Information Fund.
Read full post at:
https://desulf.blogspot.com/2020/04/starting-down-startup-path-part-11-of.html
Starting Down the Startup Path (Part 12 of a series): Patent Prior Art Search
Prior Art Search: Everything you need to know
If you’re looking to understand everything about prior art search, you’ve landed on the right page. By the time you finish reading this guide, you’ll likely have built a solid understanding of what can be included in the prior art, how you can use this knowledge to conduct a patent search all by yourself and avoid spending valuable resources on the non-patentable subject matter.
Read full post at:
https://desulf.blogspot.com/2020/04/starting-down-startup-path-part-12-of.html
Starting Down the Startup Path (Part 13 of a series) Dibenzothiophene Patents 2020
What’s the quickest way to determine if a patent is of interest to you? Depends on your purpose. This tip sheet may help you decide which section of a patent to focus on.
Read full post at:
https://desulf.blogspot.com/2020/05/starting-down-startup-path-part-13-of.html
Starting Down the Startup Path (Part 14 of a series)-Google Patents Find Prior Art Link
Patent research is important in any area of research you are engaged in ... especially if you are a startup, or are considering investing in a startup.
Prior art is an important concept in patent research.
In this regard, Google® Patents Prior Art Link is useful. When you find a patent of interest, in the upper right of the screen you will find a link labeled Prior Art.
Read full post at:
http://desulf.blogspot.com/2020/05/starting-down-startup-path-part-14-of.html
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Google® Better!
Jean Steinhardt served as Librarian, Aramco Services, Engineering Division, for 13 years. He now heads Jean Steinhardt Consulting LLC, producing the same high quality research that he performed for Aramco.
Follow Jean’s blog at: http://desulf.blogspot.com/ for continuing tips on effective online research
Email Jean at research@jeansteinhardtconsulting.com with questions on research, training, or anything else
Visit Jean’s Web site at http://www.jeansteinhardtconsulting.com/ to see examples of the services we can provide
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