Selective hydrogenation catalyst and methods of making and using same

Patent metadata

Field	Value
Publication number	US-9511359-B2
Application number	US-201414541672-A
Country	US
Kind code	B2
Filing date	Nov 14, 2014
Priority date	Nov 14, 2014
Publication date	Dec 6, 2016
Grant date	Dec 6, 2016

Abstract

A method of making a selective hydrogenation catalyst comprising contacting a support with a palladium-containing compound to form a supported-palladium composition; contacting the supported-palladium composition with an organophosphorus compound and a weak acid to form a catalyst composition; and reducing the catalyst composition to form the catalyst. A method of making a selective hydrogenation catalyst comprising contacting an alumina support with a palladium-containing compound to form a supported-palladium composition; contacting the supported-palladium composition with silver nitrate and potassium fluoride to form a mixture; contacting the mixture with an organophosphorus compound and a weak acid to form a catalyst precursor; and reducing the catalyst precursor to form the catalyst.

First claim

What is claimed is:

1. A method of making a selective hydrogenation catalyst comprising:
contacting a support with a palladium-containing compound to form a supported-palladium composition;
contacting the supported-palladium composition with an organophosphorus compound and a weak acid to form a selective hydrogenation catalyst composition, wherein the weak acid is present in an amount to provide a weak acid to organphosphorus compound molar ratio from 1:1 to 3:1; and
reducing the selective hydrogenation catalyst composition to form the selective hydrogenation catalyst.

2. The method of claim 1 wherein the organophosphorus compound is represented by the general formula (R) x (OR′) y P═O, wherein x and y are integers ranging from 0 to 3 and x plus y equals 3, wherein each R is hydrogen, a hydrocarbyl group, or combinations thereof; and wherein each R′ is a hydrocarbyl group.

3. The method of claim 1 wherein the organophosphorus compound comprises a phosphine oxide, a phosphinate, a phosphonate, a phosphate, or combinations thereof.

4. The method of claim 1 wherein the organophosphorus compound is a product of an organophosphorus compound precursor represented by the general formula of (R) x (OR′) y P, wherein x and y are integers ranging from 0 to 3 and x plus y equals 3, wherein each R is hydrogen, a hydrocarbyl group, or combinations thereof; and wherein each R′ is a hydrocarbyl group.

5. The method of claim 4 wherein the organophosphorus compound precursor comprises a phosphite, a phosphonite, a phosphinite, a phosphine, an organic phosphine, or combinations thereof.

6. The method of claim 1 wherein the organophosphorus compound has a boiling point of greater than about 100° C.

7. The method of claim 1 wherein the organophosphorus compound has a boiling point of equal to or less than about 100° C.

8. The method of claim 1 wherein the weak acid comprises boric acid, carboxylic acids, or combinations thereof.

9. The method of claim 1 wherein the weak acid comprises acrylic acid, methacrylic acid, malonic acid, succinic acid, salicylic acid, adipic acid, maleic acid, malic acid, oleic acid, gallic acid, tartaric acid, citric acid, formic acid, acetic acid, glycolic acid, oxalic acid, tartaric acid, dextotartaric acid, mesotartaric acid, propionic acid, phthalic acid, isophthalic acid, glutaric acid, gluconic acid, lactic acid, aspartic acid, glutaminic acid, itaconic acid, trifluoroacetic acid, barbituric acid, cinnamic acid, benzoic acid, 4-hydroxyhenzoic acid, aminobenzoic; a phenol, pyrogallol (benzene-1,2,3-triol), pyrocatechol (benezenediol), organoboronic acids, or combinations thereof.

10. The method of claim 1 wherein the weak acid is characterized by an acid dissociation constant pKa value in the range of from about 2 to about 12 in water.

11. The method of claim 1 wherein the weak acid is present in an amount of from about 0.00016 wt. % to about 0.16 wt. % based on the weight of hydrogen in dissociated proton form of the weak acid used to the total weight of the selective hydrogenation catalyst.

12. The method of claim 1 wherein:
the palladium-containing compound is present in an amount of from about 0.005 wt. % to about 5 wt. % Pd based on the total weight of the selective hydrogenation catalyst; and
the organophosphorus compound is present in an amount of from about 0.005 wt. % to about 5 wt. % based on the total weight of the selective hydrogenation catalyst.

13. The method of claim 1 wherein the selective hydrogenation catalyst comprises one or more selectivity enhancers.

14. The method of claim 13 wherein the one or more selectivity enhancers is selected from the group consisting of Group 1B metals, Group 1B metal compounds, silver compounds, fluorine, fluoride compounds, sulfur, sulfur compounds, alkali metal, alkali metal compounds, alkaline earth metals, alkaline earth metal compounds, iodine, iodide compounds, and combinations thereof.

15. The method of claim 14 wherein the silver compounds comprise elemental silver, silver nitrate, silver acetate, silver bromide, silver chloride, silver iodide, silver fluoride, or combinations thereof.

16. The method of claim 13 wherein the selectivity enhancer is present in an amount of from about 0.005 wt. % to about 5 wt. % based on weight of the support.

17. The method of claim 14 wherein the alkali metal compounds comprise elemental alkali metal, alkali metal fluoride, alkali metal chloride, alkali metal bromide, alkali metal iodide, alkali metal oxide, alkali metal carbonate, alkali metal sulfate, alkali metal phosphate, alkali metal borate, potassium fluoride, or combinations thereof.

18. The method of claim 17 wherein the alkali metal compound is present in an amount of from about 0.01 wt. % to about 5 wt. % based on the total weight of the selective hydrogenation catalyst.

19. The method of claim 1 further comprising drying the selective hydrogenation catalyst precursor at a temperature of from about 0° C. to about 150° C. for a time period of from about 0.1 hour to about 100 hours.

20. The method of claim 1 wherein the support comprises one or more aluminas, silicas, titanias, zirconias, aluminosilicates, spinels, or combinations thereof.

21. A selective hydrogenation catalyst prepared according to the method of claim 1 .

22. A composition comprising:
(i) a supported hydrogenation catalyst comprising palladium and a support, wherein the supported hydrogenation catalyst is capable of selectively hydrogenating highly unsaturated hydrocarbons to unsaturated hydrocarbons, the support has a surface area of from about 2 m 2 /g to about 100 m 2 /g, and greater than about 90 wt. % of the palladium is concentrated near a periphery of the support; and
(ii) an organophosphorus compound and a weak acid, wherein the weak acid is present in an amount to provide a weak acid to organophosphorus compound molar ratio from 1:1 to 3:1.

23. The composition of claim 22 wherein the organophosphorus compound comprises a phosphine oxide, phosphinate, phosphonate, phosphate, or combinations thereof.

24. The composition of claim 22 wherein the organophosphorus compound is a product of an organophosphorus compound precursor represented by the general formula of (R) x (OR′) y P, wherein x and y are integers ranging from 0 to 3 and x plus y equals 3, wherein each R is hydrogen, a hydrocarbyl group, or combinations thereof; and wherein each R′ is a hydrocarbyl group.

25. The composition of claim 24 wherein the organophosphorus compound precursor comprises a phosphite, a phosphonite, a phosphinite, a phosphine, an organic phosphine, or combinations thereof.

26. The composition of claim 22 further comprising Group 1B metals, Group 1B metal compounds, silver compounds, fluorine, fluoride compounds, sulfur, sulfur compounds, alkali metal, alkali metal compounds, alkaline earth metals, alkaline earth metal compounds, iodine, iodide compounds, or combinations thereof.

27. The composition of claim 23 wherein the phosphine oxide comprises tributylphosphine oxide, triethylphosphine oxide, triheptylphosphine oxide, trimethylphosphine oxide, trioctylphosphine oxide, tripentylphosphine oxide, tripropylphosphine oxide, triphenylphosphine oxide, or combinations thereof.

28. The composition of claim 22 wherein the weak acid comprises boric acid, carboxylic acids, or combinations thereof.

29. The compos

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Cheung Tin-Tack Peter
• Hong Zongxuan
• Bergmeister Iii Joseph

Classifications

• B01J2231/645

  of C=C or C-C triple bonds · CPC title

• B01J21/02

  Boron or aluminium; Oxides or hydroxides thereof · CPC title

• B01J23/44

  Palladium · CPC title

• B01J31/0267

  Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen · CPC title

• B01J31/0209

  Esters of carboxylic or carbonic acids · CPC title