Biomass catalytic cracking catalyst and process of preparing the same
View Patent ↗A process for producing catalyst for biomass catalytic cracking is disclosed herein. The process includes modifying a phyllosilicate to produce a modified phyllosilicate having an improved yield of a pyrolysis reaction. The modification of the phyllosilicate includes leaching the clay with an acid or basic solution to form a leached clay preparation, calcining the leached clay and contacting the treated clay with a suspension comprising metal ions for ion-exchange. The modified clay catalyst can then be mixed with inorganic materials such as zeolites and dried to form fluidizable microspheres.
1. A biomass catalytic cracking catalyst produced by the steps comprising:
a. modifying a phyllosilicate to produce a modified phyllosilicate having an improved yield when used in a biomass pyrolysis reaction, wherein the step of modifying comprises:
i. leaching the phyllosilicate to form a leached phyllosilicate preparation;
ii. calcining the leached phyllosilicate preparation forming a treated phyllosilicate;
iii. contacting the treated phyllosilicate with a suspension comprising metal ions forming a modified phyllosilicate;
b. mixing the modified phyllosilicate with inorganic materials forming a mixture wherein the inorganic materials are selected from the group consisting of metal oxides, synthetic clays, equilibrium cracking catalysts, fly ash, and cement flint; and
c. shaping the mixture into fluidizable microspheres,
wherein the catalyst comprises spinels, mixed metal oxide or a combination thereof.
2. A process to produce a biomass catalytic cracking catalyst consisting of:
a. modifying a phyllosilicate to produce a modified phyllosilicate having an improved yield when used in a pyrolysis reaction, wherein the step of modifying comprises:
(i) leaching the phyllosilicate to form a leached phyllosilicate preparation;
(ii) calcining the leached phyllosilicate preparation forming a treated phyllosilicate;
(iii) contacting the treated phyllosilicate with a suspension comprising metal ions forming a modified phyllosilicate;
b. mixing the modified phyllosilicate with inorganic materials forming a mixture wherein the inorganic materials are selected from the group consisting of metal oxides, synthetic clays, equilibrium cracking catalysts, fly ash, and cement flint; and
c. shaping the mixture into fluidizable microspheres.
3. The process of claim 2 wherein the leaching of the phyllosilicate in step (i) includes treating with an acid to remove at least part of its alumina content thereby forming an acid leached phyllosilicate preparation or treating with a base to remove at least part of its silica content thereby forming a base leached phyllosilicate preparation.
4. The process of claim 2 wherein the phyllosilicate is selected from the group consisting of smectite, bentonite, montmorillonite, beidellite, kaolinite and mixtures thereof.
5. The process of claim 4 wherein the smectite is a non-swelling smectite.
6. The process of claim 2 wherein the metal ions are selected from the group of trivalent cations, divalent cations, monovalent cations, and combination thereof.
7. The process of claim 6 wherein
the trivalent cations are selected from the group of Al, Ga, Bi, Fe, Cr, Co, Sc, La, Ce and combinations thereof,
the divalent cations are selected from the group of Mg, Ca, Zn, Ba, Mn, Co, Mo, Ni, Cu and Sr and combinations thereof, and
the monovalent cations are selected from the group of Na and K.
8. The process of claim 2 wherein the phyllosilicate is delaminated prior to the leaching step (i).
9. The process of claim 2 wherein the resulting catalyst is a mixed metal oxide or spinel.
10. The process of claim 2 wherein the step of calcining comprises heating the phyllosilicate at a temperature between about 200° C. and about 1000° C.
11. The process of claim 2 wherein the step of modifying further comprises rehydrating the treated phyllosilicate prior to contacting with the suspension.
12. The process of claim 2 wherein the step of shaping comprises spray drying the mixture to form microsphere particles suitable for biomass catalytic cracking.
13. The process of claim 12 wherein the microspheres are prepared in the presence of binders.
14. The process of claim 13 wherein the binder is selected from the group of sodium silicate, silica, silica-alumina, alumina and phosphate.
15. The process of claim 13 wherein the binder comprises phosphates.
16. The process of claim 2 wherein the phyllosilicate is kaolinite and the step of modifying further comprises delaminating the kaolinite.
17. The process of claim 2 wherein the catalyst has a reduced coke yield when used in biomass pyrolysis.
18. The process of claim 2 wherein the catalyst has a reduced oxygenated product yield when used in biomass pyrolysis.
19. The process of claim 2 wherein the catalyst has an improved bio-oil yield when used in biomass pyrolysis.
20. The process of claim 2 wherein in the step of mixing the inorganic material is a metal oxide selected from the group consisting of MgO, CaO, ZnO, CeO, Al 2 O 3 or a mixture thereof.