Catalysts For Thermo-Catalytic Conversion Of Biomass, And Methods Of Making and Using
Disclosed are catalyst compositions including zeolite and silica components, methods of making, and processes of using in the thermo-catalytic conversion of biomass. Such disclosed methods of making include treating the zeolite with phosphorous during formation of the catalyst rather than prior to or after catalyst formation.
1 . A method of preparing a biomass conversion catalyst comprising:
a) combining the following components in a mix vessel:
a phosphorous compound,
a zeolite,
a clay, and
an aqueous silica precursor to thereby form an aqueous slurry;
b) spray drying the aqueous slurry to thereby form spray dried particles; and
c) calcining the spray dried particles to thereby form the biomass conversion catalyst.
2 . The method of claim 1 wherein the aqueous slurry comprises: in the range of from about 1 to about 20 wt % of the phosphorous compound, in the range of from about 10 to about 40 wt % of the zeolite, in the range of from about 30 to about 60 wt % of the clay, and in the range of from about 10 to about 30 wt % of the aqueous silica precursor.
3 . The method of claim 1 wherein the zeolite comprises a member selected from the group consisting of: i) an 8 membered zeolite, ii) a 10 membered zeolite, iii) a 12 membered zeolite, iv) ZSM-5, v) USY, vi) mordenite, vii) ferrierite, viii) beta zeolite, and ix) mixtures thereof.
4 . The method of claim 1 wherein the zeolite comprises ZSM-5.
5 . The method of claim 1 wherein the aqueous silica precursor comprises silicic acid, polysilicic acid, and combinations thereof.
6 . The method of claim 1 wherein the aqueous silica precursor is substantially sodium free.
7 . The method of claim 1 wherein the phosphorous compound comprises a member selected from the group consisting of monoammonium phosphate, diammonium phosphate, phosphoric acid, and combinations thereof.
8 . The method of claim 1 wherein the clay comprises kaolin clay.
9 . The method of claim 1 wherein the calcining of the spray dried particles in step c) is at a temperature in the range of from about 300° C. to about 600° C.
10 . The method of claim 1 wherein the biomass conversion catalyst comprises phosphorous promoted zeolite.
11 . The method of claim 10 wherein the zeolite is promoted with phosphorous contained in the phosphorous compound to thereby form the phosphorous promoted zeolite.
12 . The method of claim 1 wherein the biomass conversion catalyst is free of or substantially free of amorphous alumina.
13 . The method of claim 1 wherein the biomass conversion catalyst comprises phosphated alumina.
14 . The method of claim 13 wherein the clay comprises alumina and wherein the alumina of the clay reacts with phosphorous contained in the phosphorous compound to thereby form the phosphated alumina.
15 . The method of claim 1 wherein the phosphorous compound is in the aqueous form and wherein the aqueous slurry is formed by:
i) adding the phosphorous compound to the mix vessel;
ii) adding the zeolite to the phosphorous compound in the mix vessel thereby forming a mixture A;
iii) adding the clay to the mixture A thereby forming a mixture B; and
iv) adding the aqueous silica precursor to the mixture B thereby forming the aqueous slurry of step a).
16 . The method of claim 15 wherein the pH of the mixtures A and B are each from about 3 to about 7.
17 . The method of claim 15 wherein the mixture A, or the mixture B, or both the mixture A and the mixture B is/are aged at a temperature of about 10 to about 50° C. for a period ranging from about 1 minute to about 24 hours.
18 . The method of claim 15 wherein the pH of the aqueous slurry is from about 2 to about 4.
19 . The method of claim 1 wherein the phosphorous compound is in the aqueous form and wherein the aqueous slurry is formed by:
i) adding the phosphorous compound to the mix vessel;
ii) adding the clay to the phosphorous compound in the mix vessel thereby forming a mixture C;
iii) adding the zeolite to the mixture C thereby forming a mixture D; and
iv) adding the aqueous silica precursor to the mixture D thereby forming the aqueous slurry of step a).
20 . The method of claim 19 wherein the pH of the mixtures C and D are each from about 3 to about 7.
21 . The method of claim 19 wherein the mixture C, or the mixture D, or both the mixture C and the mixture D is/are aged at a temperature of about 10 to about 50° C. for a period ranging from about 1 minute to about 24 hours.
22 . The method of claim 19 wherein the pH of the aqueous slurry is from about 2 to about 4.
23 . The method of claim 1 wherein the phosphorous compound is in the aqueous form and wherein the aqueous slurry is formed by:
i) combining a portion of the phosphorous compound with the zeolite outside of the mix vessel thereby forming a mixture E;
ii) combining a portion of the phosphorous compound with the clay outside of the mix vessel thereby forming a mixture F;
ii) combining the mixtures E and F in the mix vessel thereby forming a mixture G; and
iv) adding the aqueous silica precursor to the mixture G in the mix vessel thereby forming the aqueous slurry of step a).
24 . The method of claim 23 wherein the pH of the mixtures E, F, and G are each from about 3 to about 7.
25 . The method of claim 23 wherein the mixture E, or the mixture F, or both the mixture E and the mixture F is/are aged at a temperature of about 10 to about 50° C. for a period ranging from about 1 minute to about 24 hours.
26 . The method of claim 23 wherein the pH of the aqueous slurry is from about 2 to about 4.
27 . The method of claim 1 wherein the phosphorous compound is in the aqueous form and wherein the aqueous slurry is formed by:
i) adding the phosphorous compound to the mix vessel;
ii) combining a portion of the aqueous silica precursor with the zeolite outside of the mix vessel thereby forming a mixture H;
iii) combining a portion of the aqueous silica precursor with the clay outside of the mix vessel thereby forming a mixture I; and
iv) adding the mixtures H and I to the phosphorous compound in the mix vessel thereby forming the aqueous slurry.
28 . The method of claim 27 wherein the pH of the mixtures H and I are each from about 2 to about 4.
29 . The method of claim 27 wherein the mixture H, or the mixture I, or both the mixture H and the mixture I is/are aged at a temperature of about 0 to about 20° C. for a period ranging from about 1 minute to about 12 hours.
30 . The method of claim 27 wherein the pH of the aqueous slurry is from about 2 to about 4.
31 . A biomass conversion catalyst prepared by the method of claim 1 .
32 . A biomass conversion catalyst prepared by the method of claim 15 .
33 . A biomass conversion catalyst prepared by the method of claim 19 .
34 . A biomass conversion catalyst prepared by the method of claim 23 .
35 . A biomass conversion catalyst prepared by the method of claim 27 .