HYBRID SILICA AND ALUMINA AS CATALYST MATRIX AND/OR BINDER IN BIOMASS CONVERSION CATALYSTS AND BIO-OIL UPGRADING
The invention relates to catalyst compositions and components thereof for use in a catalytic process, and more particularly in a catalytic pyrolysis process or gasification of solid biomass material. In one aspect, a catalyst component is provided. The catalyst component includes a hybrid silica-alumina having a controlled Lewis acidity, and having a controlled porosity providing optimized accessibility for reactants.
1 . A catalyst component, comprising hybrid silica-alumina having a controlled Lewis acidity, and having a controlled porosity providing optimized accessibility for reactants.
2 . The catalyst component of claim 1 , wherein the catalyst component is a catalyst matrix material.
3 . The catalyst component of claim 1 , wherein the catalyst component is a catalyst binder providing structural strength and attrition resistance to a catalyst composition.
4 . The catalyst component of claim 1 , wherein the hybrid silica-alumina is one or more of silica doped alumina, alumina doped silica, silicoaluminate, and any mixture thereof.
5 . The catalyst component of claim 4 , wherein the silica doped alumina includes alumina particles and silica, wherein at least a portion of the silica is distributed in pores in the alumina particles.
6 . The catalyst component of claim 4 , wherein the silica doped alumina includes alumina particles and silica, wherein at least a portion of the silica is doped on a surface of the alumina particles.
7 . The catalyst component of claim 4 , wherein the alumina doped silica includes alumina and silica, wherein the alumina is dispersed and doped on a surface of the silica.
8 . The catalyst component of claim 4 , wherein the silicoaluminate includes alumina and silica, wherein the alumina is atomically dispersed in matrices in the silica.
9 . The catalyst component of claim 1 , wherein the controlled Lewis acidity includes suppressed density of Lewis acid sites in the hybrid silica-alumina.
10 . The catalyst component of claim 1 , wherein the controlled porosity is generated by using a pore regulating agent.
11 . A catalyst composition for biomass catalytic cracking, comprising:
a zeolite;
a binder;
a clay; and
a catalyst matrix comprising the catalyst component of claim 1 .
12 . The catalyst composition of claim 11 wherein the binder is one or both of a silica material and the catalyst component of claim 1 .
13 . The catalyst composition of claim 11 wherein the clay is kaolin and the zeolite is ZSM-5.
14 . The catalyst composition of claim 13 wherein the zeolite is phosphorous promoted.
15 . A composition for biomass conversion, comprising:
the catalyst composition of claim 11 ; and
a biomass feedstock having a carbon 14 C isotope content of about 107 pMC.
16 . A process for preparing a catalyst composition comprising:
(a) producing a hybrid silica-alumina by a method selected from the group consisting of:
i) doping silica in pores in alumina particles to form silica doped alumina; ii) doping silica on a surface of alumina particles to form silica doped alumina; iii) doping alumina on a surface of silica to form alumina doped silica; iv) atomically dispersing alumina in matrices in silica to form silicoaluminate; and combinations thereof;
(b) preparing a slurry by mixing a catalyst matrix material comprising the hybrid silica-alumina, a zeolite, a binder, and a pore regulating agent;
(c) shaping the slurry to shaped bodies; and
(d) removing the pore regulating agent from the shaped bodies, thereby producing a catalyst composition having the catalyst matrix material, the zeolite catalyst, and the binder, wherein the catalyst composition has a matrix phase having a hierarchical mesoporous-macroporous structure.
17 . A process for making a biomass conversion catalyst comprising:
a) mixing an aqueous silica precursor and an alumina-containing component thereby forming a slurry A;
b) adding a phosphorous-promoted zeolite and a clay to the slurry A thereby forming a slurry B;
c) shaping the slurry B thereby forming shaped bodies; and
d) calcining the shaped bodies thereby forming the biomass conversion catalyst.
18 . The process of claim 17 , wherein a pore regulating agent is also added to the slurry B.
19 . The process of claim 17 wherein the aqueous silica precursor of the slurry A comprises polysilicic acid, and wherein the alumina-containing component is peptized by the polysilicic acid thereby forming a hybrid binder system.
20 . The process of claim 19 , wherein the slurry A is aged for a period of about 10 minutes to about 2 hours.
21 . The process of claim 17 wherein the alumina-containing component comprises an acid peptized alumina compound.
22 . The process of claim 21 , wherein the acid-peptized alumina compound is prepared by mixing an acid with an alumina-containing compound.
23 . The process of claim 22 , wherein the alumina-containing compound is selected from the group consisting of kaolin, boehmite, pseudoboehmite, or any combination thereof.
24 . The process of claim 22 , wherein the acid is selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and combinations thereof.
25 . The process of claim 17 wherein the shaped bodies are calcined in step d) without washing before or after.
26 . The process of claim 19 , wherein the hybrid binder system is one or more of silica doped alumina, alumina doped silica, silicoaluminate, and any mixture thereof.
27 . The process of claim 26 , wherein the silica doped alumina comprises alumina particles and silica, wherein the silica is distributed in pores in the alumina particles.
28 . The process of claim 26 , wherein the silica doped alumina comprises alumina particles and silica, wherein the silica is doped on a surface of the alumina particles.
29 . The process of claim 26 , wherein the alumina doped silica comprises alumina and silica, wherein the alumina is dispersed and doped on a surface of the silica.
30 . The process of claim 26 , wherein the silicoaluminate comprises alumina and silica, wherein the alumina is atomically dispersed in matrices in the silica.
31 . The process of claim 17 , wherein the pHs of the slurry A and the slurry B are in the range of from about 1.5 to about 3.5.
32 . The process of claim 17 , wherein the biomass conversion catalyst has less than about 0.02 cm 3 /g pore volume of the mesopores in the range of 20-100 Å.
33 . The process of claim 18 , wherein the biomass conversion catalyst has greater than about 0.04 cm 3 /g pore volume of the mesopores in the range of 20-100 Å.
34 . A process for making a biomass conversion catalyst comprising:
a) utilizing a slurry C comprising an aqueous silica precursor;
b) adding a phosphorous-promoted zeolite and a clay to the slurry C thereby forming a slurry D;
c) adding an acid-peptized alumina compound to the slurry D thereby forming a slurry E;
d) shaping the slurry E thereby forming shaped bodies; and
e) without washing before or after, calcining the shaped bodies thereby forming the biomass conversion catalyst.
35 . The process of claim 34 , wherein the acid-peptized alumina compound is prepared by mixing an acid with an alumina-containing compound.
36 . The process of claim 35 , wherein the acid is selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid, and combinations thereof.
37 . The process of claim 35 , wherein the alumina-containing compound is selected from the group consisting of kaolin, boehmite, pseudoboehmite, and combinations thereof.
38 . The process of claim 34 , wherein a pore regulating agent is also added to the slurry E.
39 . The process of claim 34 , wherein the acid-peptized alumina compound is selected from the group consisting of aluminum chlorohydrate, polyaluminum chloride, and combinations thereof.
40 . The process of claim 34 , wherein the pHs of the slurry C, the slurry D, and the slurry E are in the range of from about 1.5 to about 3.5.
41 . The process of claim 34 , wherein the biomass conversion catalyst has less than about 0.02 cm 3 /g pore volume of the mesopores in the range of from 20-100 Å.
42 . The process of claim 38 , wherein the biomass conversion catalyst has greater than about 0.04 cm 3 /g pore volume of the mesopores in the range of from 20-100 Å.