Catalyst Compositions for Use in a Two-Stage Reactor Assembly Unit for the Thermolysis and Catalytic Conversion of Biomass
Aspects of the invention relate to a catalyst system for the conversion of biomass material. In an exemplary embodiment, the catalyst system has a specific combined mesoporous and macroporous surface area in the range of from about 1 m 2 /g to about 100 m 2 /g. The catalyst system can be used in a two-stage reactor assembly unit for the catalytic thermoconversion of biomass material wherein the thermolysis process and the catalytic conversion process are optimally conducted separately.
1 . A dual function catalyst system for use in thermolysis and catalytic cracking of biomass material, the catalyst system comprising a matrix, a densifier and a catalytically active material, wherein the catalyst system has a specific combined mesoporous and macroporous surface area in the range from about 1 m 2 /g to about 100 m 2 /g.
2 . The catalyst system of claim 1 wherein the matrix comprises a clay mineral.
3 . The catalyst system of claim 1 wherein the clay is a calcined clay, a metal doped clay, an acid leached clay, a base-leached clay, a delaminated clay, a dealuminated clay, a desilicated clay or combinations thereof.
4 . The catalyst system of claim 1 wherein catalytically active material comprises a zeolite, a phosphated zeolite, a metal oxide, metal hydroxide, metal carbonate, metal hydroxyl-carbonate, metal phosphate or combinations thereof.
5 . The catalyst system of claim 4 wherein the zeolite is a MFI zeolite, a Faujasite type zeolite or combinations thereof.
6 . The catalyst system of claim 4 wherein the catalytically active material comprises a spinel form of the metal or a refractory form of the metal.
7 . The catalyst system of claim 1 wherein the densifier comprises an alpha alumina, a silica, inert oxides of transition metals, refractory clay, mullite, calcined diatomite or combinations thereof.
8 . The catalyst system of claim 1 further comprising a binder.
9 . The catalyst system of claim 8 wherein the binder comprises polysilicic acid, aluminum chlorohydrol, aluminum nitrohydrol or combinations thereof.
10 . The catalyst system of claim 2 wherein the clay mineral is the densifier.
11 . A method of making a dual function catalyst system for use in conversion of biomass material, the method comprising:
a. preparing a slurry comprising a matrix, a densifier and optionally a binder;
b. shaping the slurry into shaped bodies; and
c. subjecting the shaped bodies to calcination at a temperature ranging from about 500° C. and 1,000° C.,
wherein the dual function catalyst system has a specific combined mesoporous and macroporous surface area in the range from about 1 m 2 /g to about 100 m 2 /g.
12 . The method of claim 11 wherein the step (a) further comprises a zeolite or a non-zeolitic catalytic material.
13 . The method of claim 11 further comprising:
d. mixing the shaped bodies in water in presence of a soluble alumina source and a soluble silica source and a zeolitic seeding material to form a slurry; and
e. subjecting the slurry of step d) to a temperature of about 175° C. thereby forming in situ grown zeolites.
14 . The method of claim 13 further comprising adding a phosphorous compound before step e) or treating the shaped bodies of step b) with a phosphorous compound.
15 . A process for converting solid particulate biomass material, the process comprising:
a. providing the solid particulate biomass in a reactor;
b. thermally pyrolyzing at least a portion of the solid particulate biomass in presence of a catalyst system to form primary reactions products within a first zone of the reactor; and
c. catalytically converting at least a portion of the primary reaction products into secondary reaction products in the presence of the catalytic system within a second zone of the reactor,
wherein the catalytic system has a specific combined mesoporous and macroporous surface area in the range from about 1 m 2 /g to about 100 m 2 /g.
16 . The process of claim 15 wherein the primary products are oil, oil vapors or combination thereof.
17 . The process of claim 15 further comprising one or more of the following:
d. stripping volatile materials from deactivated catalyst system in a stripper;
e. regenerating at least part of the deactivated catalyst system in a regenerator;
f. recycling back regenerated catalyst system to the first, the second or the first and the second zone of the reactor;
g. hydrotreating the primary or secondary reaction products in a hydrotreating reactor, the hydrotreating reactor being in fluid communication with the reactor.
18 . The process of claim 17 wherein
the step of thermally pyrolyzing takes place in a first reactor and wherein the first reactor is a thermolysis reactor;
the step of catalytically converting takes place in a second reactor and wherein the second reactor is a catalytic cracking reactor;
in the step of hydrotreating, the hydrotreating reactor is a fixed bed or an ebullated bed reactor.
19 . The process of claim 15 wherein in the step of thermally pyrolyzing, the temperature in the first zone is in the range of 350° C. to 600° C. and in the step of catalytically converting the temperature in the second zone is equal or higher than the temperature in the first zone.
20 . The process of claim 15 wherein the catalyst system acts as a heat carrier in the step of thermally pyrolyzing and acts as a catalyst in the step of catalytically converting.