[미국특허]
Process for preparing V-Ti-P catalysts for synthesis of 2,3-unsaturated carboxylic acids
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
B01J-027/198
C07B-035/00
C07C-051/00
출원번호
US-0234313
(2011-09-16)
등록번호
US-8765629
(2014-07-01)
발명자
/ 주소
Norman, David William
Tustin, Gerald Charles
Nash, Michael James
Deng, Liu
Barnette, Theresa Sims
출원인 / 주소
Eastman Chemical Company
대리인 / 주소
Leonard, James K.
인용정보
피인용 횟수 :
5인용 특허 :
49
초록▼
The invention relates to a catalyst composition comprising a mixed oxide of vanadium, titanium, and phosphorus. The titanium component is derived from a water-soluble, redox-active organo-titanium compound. The catalyst composition is highly effective at facilitating the vapor-phase condensation of
The invention relates to a catalyst composition comprising a mixed oxide of vanadium, titanium, and phosphorus. The titanium component is derived from a water-soluble, redox-active organo-titanium compound. The catalyst composition is highly effective at facilitating the vapor-phase condensation of formaldehyde with acetic acid to generate acrylic acid, particularly using an industrially relevant aqueous liquid feed.
대표청구항▼
1. A catalyst composition comprising an amorphous mixed oxide of vanadium (V), titanium (Ti), and phosphorus (P), wherein the titanium component is the residue of a water-soluble, redox-active organo-titanium compound comprising titanium(IV) bis(ammonium lactate)dihydroxide. 2. The catalyst composit
1. A catalyst composition comprising an amorphous mixed oxide of vanadium (V), titanium (Ti), and phosphorus (P), wherein the titanium component is the residue of a water-soluble, redox-active organo-titanium compound comprising titanium(IV) bis(ammonium lactate)dihydroxide. 2. The catalyst composition according to claim 1, which has the general formula VTiaPbOc, wherein a is a number from 0.3 to 6.0, b is a number from 2.0 to 13.0, and c is the number of atoms required to satisfy the valences of V, Ti, and P. 3. The catalyst composition according to claim 2, wherein a ranges from 1.0 to 4.0, and b ranges from 4.0 to 10.0. 4. The catalyst composition according to claim 1, which further comprises a pre-shaped support. 5. The catalyst composition according to claim 4, wherein the pre-shaped support comprises silica, alumina, titanium oxide, titanium pyrophosphate, zirconium oxide, or zirconium pyrophosphate. 6. The catalyst composition according to claim 4, wherein the pre-shaped support has a particle size ranging from 0.1 mm to 20 mm. 7. A method for preparing an amorphous catalyst composition comprising a mixed oxide of vanadium (V), titanium (Ti), and phosphorus (P); wherein the method comprises: (a) providing an aqueous solution comprising a water-soluble, redox-active organo-titanium compound comprising titanium(IV) bis(ammonium lactate)dihydroxide;(b) adding a vanadium compound and a phosphorus compound to the aqueous titanium solution to form a mixture of catalyst components;(c) heat-treating the mixture;(d) removing water from the heat-treated mixture to obtain a solid residue comprising the catalyst components; and(e) calcining the solid residue at an elevated temperature in the presence of air to obtain the catalyst composition. 8. The method according to claim 7, wherein the water removing step (d) comprises distillation or evaporation. 9. The method according to claim 7, wherein the water removing step (d) comprises adding an anti-solvent to the mixture to precipitate out the catalyst components and separating the precipitate from the liquid to obtain the solid residue. 10. The method according to claim 9, wherein the precipitate is separated from the liquid by filtration. 11. The method according to claim 9, wherein the anti-solvent is a polar compound selected from alcohols, ketones, aldehydes, ethers, and esters. 12. The method according to claim 9, wherein the anti-solvent is an alcohol. 13. The method according to claim 7, wherein the catalyst composition has the general formula VTiaPbOc, wherein a is a number from 0.3 to 6.0, b is a number from 2.0 to 13.0, and c is the number of atoms required to satisfy the valences of V, Ti, and P. 14. The method according to claim 13, wherein a ranges from 1.0 to 4.0, and b ranges from 4.0 to 10.0. 15. The method according to claim 7, wherein the catalyst composition further comprises a pre-shaped support. 16. The method according to claim 15, wherein the pre-shaped support is added to the mixture of catalyst components before the heat-treating step (c). 17. The method according to claim 7, which further comprises adding a bifunctional compound to the mixture of catalyst components before the heat-treating step (c), wherein the bifunctional compound comprises citric acid, lactic acid, glycolic acid, oxalic acid, ethylene glycol, butane diol, pentane diol, or hexane diol. 18. The method according to claim 17, wherein the bifunctional compound comprises lactic acid. 19. A process for preparing a 2,3-unsaturated carboxylic acid, comprising: contacting a formaldehyde source with a carboxylic acid in the presence of a condensation catalyst under vapor-phase condensation conditions to obtain the 2,3-unsaturated carboxylic acid,wherein the condensation catalyst comprises an amorphous mixed oxide of vanadium (V), titanium (Ti), and phosphorus (P), andwherein the titanium component is the residue of a water-soluble, redox-active organo-titanium compound comprising titanium(IV) bis(ammonium lactate)dihydroxide. 20. The process according to claim 19, wherein the formaldehyde source comprises formaldehyde, 1,3,5-trioxane, dimethoxymethane, or diacetoxymethane, and the carboxylic acid comprises acetic acid or propionic acid. 21. The process according to claim 19, wherein the formaldehyde source comprises an aqueous solution of formaldehyde, 1,3,5-trioxane, dimethoxymethane, or diacetoxymethane, and the carboxylic acid comprises acetic acid or propionic acid. 22. The process according to claim 21, wherein the aqueous solution comprises from 30 to 65 weight percent of formaldehyde. 23. The process according to claim 19, wherein the catalyst composition further comprises a pre-shaped support. 24. The process according to claim 19, wherein the condensation conditions comprise a total feed space velocity of from 50 to 400 moles of feed/(kg catalyst·hr). 25. The process according to claim 24, wherein the total feed space velocity ranges from 100 to 300 moles of feed/(kg catalyst·hr). 26. The process according to claim 25, wherein the total feed space velocity ranges from 125 to 200 moles of feed/(kg catalyst·hr).
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