NZ624597B2 - A catalyst for producing hydrocarbons - Google Patents
A catalyst for producing hydrocarbons Download PDFInfo
- Publication number
- NZ624597B2 NZ624597B2 NZ624597A NZ62459712A NZ624597B2 NZ 624597 B2 NZ624597 B2 NZ 624597B2 NZ 624597 A NZ624597 A NZ 624597A NZ 62459712 A NZ62459712 A NZ 62459712A NZ 624597 B2 NZ624597 B2 NZ 624597B2
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- NZ
- New Zealand
- Prior art keywords
- catalyst
- velocity
- char
- bed
- products
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- 239000003054 catalyst Substances 0.000 title claims abstract description 232
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 72
- 239000002184 metal Substances 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000002028 Biomass Substances 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 12
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 210000003278 egg shell Anatomy 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 88
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002154 agricultural waste Substances 0.000 claims description 2
- 238000009360 aquaculture Methods 0.000 claims description 2
- 244000144974 aquaculture Species 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000002029 lignocellulosic biomass Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 244000144977 poultry Species 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 238000009877 rendering Methods 0.000 claims description 2
- 239000010801 sewage sludge Substances 0.000 claims description 2
- 239000012717 electrostatic precipitator Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 48
- 150000002739 metals Chemical class 0.000 abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000003502 gasoline Substances 0.000 abstract description 5
- 239000012263 liquid product Substances 0.000 abstract description 5
- 239000002283 diesel fuel Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000005470 impregnation Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 12
- 238000001354 calcination Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 230000035515 penetration Effects 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000000197 pyrolysis Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910003294 NiMo Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 241000195493 Cryptophyta Species 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000002241 glass-ceramic Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- -1 diesel Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000000177 wavelength dispersive X-ray spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 230000003635 deoxygenating effect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005367 electrostatic precipitation Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010925 yard waste Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B01J35/0026—
-
- B01J35/0073—
-
- B01J35/008—
-
- B01J35/023—
-
- B01J35/08—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/72—Regeneration or reactivation of catalysts, in general including segregation of diverse particles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
Disclosed is an eggshell hydropyrolysis catalyst impregnated on a spherical alumina support. The spherical catalyst has a center region (116) and an outershell region (112) where the active metal component is located and has penetrated to a depth (114) into the support from the surface (110). Metals suitable for impregnating the spherical alumina support are nickel, cobalt, molybdenum, and combinations thereof. Also disclosed is a process using the eggshell catalyst for converting biomass into liquid products that may meet the specifications for gasoline, diesel fuel, jet fuel and/or other valuable liquid hydrocarbon products. suitable for impregnating the spherical alumina support are nickel, cobalt, molybdenum, and combinations thereof. Also disclosed is a process using the eggshell catalyst for converting biomass into liquid products that may meet the specifications for gasoline, diesel fuel, jet fuel and/or other valuable liquid hydrocarbon products.
Description
A CATALYST FOR PRODUCING HYDROCARBONS
Field of Invention
The invention relates to an improved hydropyrolysis catalyst for use in a
process for producing hydrocarbons from biomass.
Background
There is considerable interest in finding ways to convert biomass into valuable
products, especially products that can be used as transportation fuels or in other
chemical processes.
US Patent Application Publication No. 2010/0251600, which is herein
incorporated by reference, describes a multi-stage process for producing liquid
products from biomass in which the biomass is hydropyrolyzed in a reactor vessel
containing molecular hydrogen and a deoxygenating catalyst, producing a partially
deoxygenated pyrolysis liquid, char, and first stage process heat. The partially
deoxygenated pyrolysis liquid is hydrogenated using a hydroconversion catalyst,
producing a substantially fully deoxygenated pyrolysis liquid, a gaseous mixture
comprising carbon monoxide and light hydrocarbon gases (C1-C4), and second stage
process heat. The gaseous mixture is then reformed in a steam reformer, producing
reformed molecular hydrogen. The reformed molecular hydrogen is then introduced
into the reactor vessel for the hydropyrolysis of additional biomass.
Improved catalysts for use in this type of process are needed to make it
economically and technically feasible to carry out this process on a commercial scale.
It is an object of the present invention to go some way to meeting this need, and/or to
at least provide the public with a useful choice.
In this specification where reference has been made to patent specifications,
other external documents, or other sources of information, this is generally for the
purpose of providing a context for discussing the features of the invention. Unless
specifically stated otherwise, reference to such external documents is not to be
construed as an admission that such documents, or such sources of information, in
any jurisdiction, are prior art, or form part of the common general knowledge in the
art.
Summary of the Invention
The invention provides a process for converting biomass to products
comprising: contacting the biomass with hydrogen in the presence of a fluidized bed
of fresh hydropyrolysis catalyst in a reactor vessel under hydropyrolysis conditions
comprising a temperature in the range of from 270 °C to 450 °C and a pressure in the
range of from 1 MPa to 7.5 MPa.; removing products and char from the reactor vessel;
carrying out the contacting and removing steps for a period of time such that the
fresh hydropyrolysis catalyst attrits in the fluidized bed to form small catalyst
particles; and removing at least a portion of the small catalyst particles with the
products and char wherein the products leave the fluidized bed at a exit bed velocity,
the char has a settling velocity that is less than the exit bed velocity, the fresh
hydropyrolysis catalyst has a settling velocity that is greater than the exit bed
velocity, the small catalyst particles have a settling velocity that is less than the exit
bed velocity and wherein the hydropyrolysis catalyst comprises a support and an
active metal component wherein the catalyst is an eggshell type catalyst wherein at
least 60wt% of the total active metal component is located in the outer 50% of the
volume of the support.
Described herein is a hydropyrolysis catalyst comprising a support and an
active metal component wherein the catalyst is an eggshell type catalyst having the
active metal component located in the outer portion of the support.
Described herein is a hydropyrolysis catalyst comprising a support and an
active metal component wherein at least 60 wt % of the total active metal component
is located in the outer 50% of the volume of the support.
Described herein is a hydropyrolysis catalyst comprising a support and an
active metal component wherein the active metal component is distributed in an
outer shell region of the catalyst having a penetration depth of 3 to 15% of the
catalyst diameter and a remaining center of the catalyst such that the ratio of the
average concentration in the outer shell region to the average concentration in the
remaining center of the catalyst is in the range of from 1.3:1 to 6:1.
Described herein is a hydropyrolysis catalyst comprising a support and an
active metal component wherein a center of the catalyst comprises a base active
metal concentration and a remaining outer shell region of the catalyst comprises an
increased active metal concentration, the center having a diameter of at least 200 µm
and the outer shell region having a penetration depth in the range of from 40 µm to
500 µm.
Described herein is a hydropyrolysis catalyst comprising a support and an
active metal component wherein the support comprises an outer shell region and a
center region; the center region is defined as the volume of the support within 25% of
the radius of the support, the outer shell region is the volume of the support between
the outer surface and 75% of the radius of the support; and the ratio of the average
active metal concentration in the outer shell region to the average active metal
concentration in the center region is from 1.3:1 to 6.0:1.
Described herein is a process for converting biomass to products comprising:
contacting the biomass with hydrogen in the presence of a fluidized bed of
hydropyrolysis catalyst in a reactor vessel under hydropyrolysis conditions; and
removing products, char, ash, and attritted catalyst fines from the reactor vessel
wherein the hydropyrolysis catalyst is an eggshell type catalyst.
Described herein is a process for converting biomass to products comprising:
contacting the biomass with hydrogen in the presence of a fluidized bed of fresh
hydropyrolysis catalyst in a reactor vessel under hydropyrolysis conditions;
removing products, char, ash, and attritted catalyst fines from the reactor vessel;
carrying out the contacting and removing steps for a period of time such that the
fresh hydropyrolysis catalyst attrits in the fluidized bed to form small catalyst
particles; and removing at least a portion of the small catalyst particles with the
products and char wherein the products leave the fluidized bed at a exit bed velocity,
the char has a settling velocity that is less than the exit bed velocity, the fresh
hydropyrolysis catalyst has a settling velocity that is greater than the exit bed
velocity, the small catalyst particles have a settling velocity that is less than the exit
bed velocity and the hydropyrolysis catalyst is any suitable catalyst described herein.
In the description in this specification reference may be made to subject
matter which is not within the scope of the appended claims. That subject matter
should be readily identifiable by a person skilled in the art and may assist in putting
into practice the invention as defined in the appended claims.
The term “comprising” as used in this specification and claims means
“consisting at least in part of”. When interpreting statements in this specification and
claims which include the term “comprising”, other features besides the features
prefaced by this term in each statement can also be present. Related terms such as
“comprise” and “comprises” are to be interpreted in similar manner.
Brief Description of the Drawings
Figure 1 depicts the process flow of the hydropyrolysis process
Figure 2 depicts the inside of the reactor vessel during operation
Figure 3 depicts an embodiment of a suitable hydropyrolysis catalyst
Figure 4 depicts an embodiment of a suitable hydropyrolysis catalyst
Figure 5 depicts the average metal distribution of Catalyst A from Example 1
Figure 6 depicts the average metal distribution of Catalyst B from Example 1
Detailed Description
This process is used to convert biomass into liquid products that may meet the
specifications for gasoline, diesel fuel, jet fuel and/or other valuable liquid
hydrocarbon products. Biomass feeds for the hydropyrolysis reactor may include a
wide variety of plant-derived materials, including biorefinery and agricultural wastes,
lignin, lignocellulosic biomass and aquatic biomass, animal and human-derived
materials, including everything from fat from rendering plants, poultry wastes,
sewage sludge, and wastes from aquaculture such as fisheries. Preferred plant-
derived feedstocks include lignin, wood and algae. Algae may include whole algae and
algal residues, for example, residues derived after any extractive procedures to
remove lipids, proteins and/or carbohydrates. Mixtures of materials from municipal
solid waste dumps, for example, plastics, plastic residues accumulated in oceanic
gyres, paper, cardboard, yard waste, food residue, etc., may be fed to the
hydropyrolysis reactor.
It is presumed that any material which breaks down, upon rapid heating, into
oxygenated hydrocarbons and/or non-oxygenated hydrocarbons with boiling points
in the gasoline, diesel, or kerosene range could potentially be used as feedstock.
Therefore, any of the candidate feedstocks identified above, and arbitrary mixtures of
two or more of these feedstocks should be acceptable feeds for hydropyrolysis and
hydroconversion process of the invention disclosed in US Patent Application
Publication No. 2010/0251600.
The biomass feed is typically prepared for use in the reaction by sizing and
drying. The selection of biomass and the feed treatment process play a large role in
the characteristics of the char formed in the reaction.
The other primary feed to the process is hydrogen. The hydrogen may be
imported for use in the process or produced in a steam reformer. The steam reformer
may be fed light hydrocarbons (C1-C4) and carbon monoxide produced in the
hydropyrolysis process. Other gases, examples of which include CO, CO2, H2O and
H2S, may be present in trace amounts, so long as their presence does not materially
affect the high partial pressure of H2 which is required by the process.
The hydropyrolysis reaction is carried out under suitable hydropyrolysis
conditions that provide for the production of a partially deoxygenated pyrolysis
liquid, char, light hydrocarbons (C -C ) and carbon monoxide. The temperature of the
reaction may be in the range of from about 300 °C to about 600 °C, preferably in the
range of from about 350 °C to about 540 °C and more preferably in the range of from
about 399 °C to about 450 °C. The pressure of the reaction may be in the range of
from about 1.38 MPa to about 6.00 MPa, preferably in the range of from about 1.72
MPa to about 5.50 MPa, more preferably in the range of from about 2.06 MPa to about
.00 MPa and most preferably in the range of from about 2.76 MPa to about 4.14 MPa.
The hydropyrolysis catalyst in the reactor is in the form of a fluidized bed. The
velocity of the feed and products upward through the bed is sufficient to maintain the
catalyst in a fluidized state. Most of the products are in a gaseous form under the
hydropyrolysis reaction conditions and therefore pass in an upward direction
through the bed. They pass through the upper portion of the bed and exit the catalyst
bed. The velocity at which the gaseous products exit the catalyst bed is referred to
herein as the exit bed velocity. The exit bed velocity will be a result of the feed rate,
reaction rate, reactor pressure and temperature, and reactor dimensions.
In order to maintain the upper portion of the catalyst bed in the reactor, the
exit bed velocity must not be so high that the vapor entrains catalyst particles and
carries them overhead with the products. The tendency of the catalyst or other solids
formed in the reactor to be entrained with the vapor is determined by the settling
velocity of the individual particles.
The settling velocity of a particle is the terminal velocity a particle reaches
when traveling in a fluid and is achieved when the drag force of the fluid on the
particle is equal and opposite to the force of gravity on the particle. The settling
velocity of a particle is a function of the density of the particle, the diameter of the
particle, the fluid (gas) density and gravitational acceleration. See Kunii, Daizo and
Octave Levenspiel, Fluidization Engineering. 2 ed. (Butterworth-Heinemann 1991),
p. 80, which is herein incorporated by reference. The shape and other factors are
incorporated into an experimentally determined dimensionless drag coefficient.
In a fluidized bed, the settling velocity of the individual particles and the gas
velocity in the bed can be combined to arrive at a net particle velocity, i.e., the gas
velocity in the bed minus the settling velocity of the particle will be the net velocity of
the particle. For example, a char particle with a net upward velocity will be carried
out of the bed and entrained with the gaseous products because the gas velocity is
greater than the settling velocity of the char particles. On the other hand, a catalyst
particle will have a net negative (downward) velocity when the settling velocity of the
catalyst particle is greater than the gas velocity in the bed, and the catalyst particle
will tend to remain in the catalyst bed.
In this process, it is preferred for the catalyst to remain in the fluidized catalyst
bed as long as it still contains sufficient active metal component and for the majority
of the char to be entrained with the gaseous products and carried out of the reaction.
It is also preferred to allow for the catalyst to be removed once the majority of the
active metal component present on the fresh catalyst has been lost. It is important to
keep as much catalyst with the active metal component as possible in the fluidized
bed to maintain the reaction activity and prevent contamination of the char by the
metals on the catalyst.
The exit bed velocity is a function of the process conditions and the reactor
configuration. Specifically, the exit bed velocity can be calculated as the volumetric
flow rate of gaseous products exiting the bed divided by the cross sectional area of the
reactor at the top of the fluidized catalyst bed. It is preferred for the settling velocity
of the catalyst to be at least 1.5 times the settling velocity of the char to achieve an
effective separation between the char and catalyst, but the main factor in carrying out
this separation is the exit bed velocity.
The hydropyrolysis catalyst can be any supported catalyst known to one of
ordinary skill in the art to be useful in this reaction. A suitable catalyst for use in this
process has certain physical characteristics that affect its performance in the fluidized
bed hydropyrolysis reactor. In this process, the settling velocity of the catalyst
determines whether the catalyst will remain in the fluidized bed or be eluted from the
reactor and carried out with the gaseous products. If the settling velocity of the
catalyst is greater than the exit bed velocity then the catalyst will remain in the
fluidized bed and not be entrained with the gaseous products.
The settling velocity of the catalyst may be any velocity greater than the exit
bed velocity, preferably greater than 110% of the exit bed velocity, more preferably
greater than 125% of the exit bed velocity and most preferably greater than 150% of
the exit bed velocity.
A suitable catalyst for this process is a sulfided CoMo or NiMo catalyst
impregnated on a spherical alumina support. These catalysts are placed on spherical
supports to minimize attrition for use in a fluid bed reactor. Another suitable catalyst
is a nickel aluminate or nickel catalyst impregnated on a spherical alumina support. In
all cases the catalyst is selected those having enough activity to deoxygenate the
feedstock, add hydrogen to the devolatized feedstock, and minimize coking reactions.
It is possible that in addition to these catalysts, other catalysts might work as
well. Glass-ceramic catalysts can be extremely strong and attrition resistant and can
be prepared as thermally impregnated catalysts. When employed as a sulfided NiMo,
Ni/NiO, or Co based glass-ceramic catalyst, the resulting catalyst is an attrition
resistant version of a readily available, but soft, conventional NiMo, Ni/NiO, or Co
based catalyst. Glass-ceramic sulfided NiMo, Ni/NiO, or Co based catalysts are
particularly suitable for use in a hot fluidized bed because these materials can provide
the catalytic effect of a conventional supported catalyst, but in a much more robust,
attrition resistant form. In addition, due to the attrition resistance of the catalyst, the
biomass and char are simultaneously ground into smaller particles as the
hydropyrolysis reactions proceed within the hydropyrolysis reactor.
The settling velocity of the fluidized catalyst in the fluidized bed reactor will
decrease over time as the catalyst attrits due to the vigorous mixing in the fluidized
bed. When this happens it has been found that extremely small catalyst dust particles
are produced from attrition in the 1-5 micron range. Further, as the settling velocity
of the supported catalyst decreases, it will reach a point where the settling velocity of
the attritted catalyst as well as the small catalyst particles that are broken off of the
catalyst will be less than the exit bed velocity and the attritted catalyst or small
catalyst particles will be entrained and carried over with the gaseous products. These
catalysts will have different attrition rates and the rate of attrition will be a factor in
determining the hydropyrolysis catalyst to use in the reactor. A suitable catalyst is
preferably attrition resistant so this process of attrition of the catalyst will happen
very slowly.
A preferred catalyst has a majority of the active metal component on or near
the outer surface of the support. It is desirable to keep the fresh catalyst in the
fluidized bed, and then to remove the catalyst once the active metal component
remaining on the support is diminished to a point where its catalytic activity is
negligible. As the outer surface of the catalyst attrits, the active metal component is
removed from the catalyst. Once substantially all or at least a majority of the active
metal component has been removed from the support through attrition, the
remaining catalyst support should have a settling velocity that is lower than the exit
bed velocity. Then the support with substantially no active metal component will be
eluted from the process and new catalyst can be added as needed. In this way, the
system is designed so that active catalyst is retained in the reactor, but once it has lost
most or all of its activity due to loss of the active metal component from the surface,
the catalyst support is removed with the char via the overhead product line.
To make a catalyst that has an active metal component disposition profile such
that the catalyst is an eggshell type catalyst, any method known to those of skill in the
art can be used. Embodiments of suitable methods will be described hereinafter and
suitable catalysts will also be described hereinafter.
One method of preparing a suitable catalyst is described in US 7,087,191,
which is herein incorporated by reference. The patent describes a method of making a
shell metal catalyst which has a large quantity of the catalytically-active metal
dispersed in the outer layer of the catalyst particles. The method comprises the steps
of (1) applying a slurry comprising a diluent, a catalytically active metal or a
precursor compound thereof, and optionally a refractory oxide of an element having
an atomic number of at least 20 or a precursor of the first refractory oxide, onto the
surface of particles of a core carrier, forming a wet coating, and (2) removing at least
a part of the diluent from the wet coating, wherein the slurry comprises at least 5% w
of the catalytically active metal or the precursor compound thereof, calculated on the
weight of the metal relative to the weight of calcination residue which can be formed
from the slurry by drying the slurry and calcining.
Further, in describing the thickness of the wet coating formed on the support,
the patent provides that the thickness of the wet coating is suitably such that after
drying and calcining in accordance with the standard conditions as defined
hereinbefore, the thickness of the remaining coating meets certain criteria. A first
criterion may be that the largest thickness of the remaining coating is less than 0.2
mm, which means that there is no remaining coating which is thicker than 0.2 mm. In
particular, the largest thickness is in the range of form 0.002 to 0.15 mm, more in
particular in the range of from 0.005 to 0.1 mm. An independent second criterion may
be that the average thickness of the remaining coating is in the range of from 0.001 to
0.15 mm, preferably in the range of from 0.002 to 0.1 mm, in particular in the range of
from 0.005 to 0.08 mm. The average thickness as quoted is defined as the quotient of
the total volume of the remaining coating (i.e. after drying and calcining in accordance
with the said standard conditions) and the external surface area of the core particles.
The average thickness so defined is deemed to relate to a relatively large number of
particles, say for the particles present in a dumped bed of 1 m volume.
A preferred method of preparing the catalyst is impregnation of a shaped
porous substrate with a solution containing catalytically active metals. The
impregnated substrate is then heat treated. The desired metal distribution range may
be achieved by appropriate solution chemistry and an appropriate heat treatment
process.
In one embodiment, the catalyst is made by subjecting a support to at least two
impregnations, preferably by spraying, with a nickel containing solution. Each
impregnation step is followed by a drying step to release a nickel precursor from the
solution and a calcination step to convert the nickel precursor to nickel crystallites.
It is believed that impregnation by spraying, particularly in combination with
relatively mild drying and calcination enables the production of catalysts with an
eggshell type distribution of metals.
In one embodiment, a catalyst is prepared by spraying an ammoniacal solution
of a nickel salt onto an alumina or silica-alumina support. The volume of the
ammoniacal solution used for impregnation may be from 100 to 115%, preferably
110 to 115% of the pore volume of the support. Further, the volume of the
ammoniacal solution used in a subsequent impregnation may be from 100 to 115%,
preferably 110 to 115% of the pore volume of the impregnated, dried and calcined
intermediate.
In another embodiment, a catalyst may be prepared by at least three
impregnation steps. This embodiment is used to produce catalysts having a nickel
loading of greater than 24 wt% or catalysts having a total metal loading of greater
than 19 wt%.
The ammoniacal solution of a nickel salt may be produced by dissolving
Ni(OH) and/or NiCO in ammonia and/or ammonium carbonate and or ammonium
hydrogen carbonate. In one embodiment, the nickel concentration of the solution
may be from 100 to 200 g Ni/l, preferably from 110 to 190 g Ni/l and more preferably
from 120 to 180 g Ni/l.
The drying step(s) conducted after each impregnation are preferably carried
out at from 80 to 200 °C, more preferably from 90 to 140 °C, and most preferably
from 100 to 130 °C. The drying time is at least 30 minutes, preferably at least 1 hour
and more preferably at least 3 hours.. The drying time may be at most 24 hours,
preferably at most 12 hours and more preferably at most 6 hours.
The calcination step(s) conducted after each drying step are preferably carried
out at from 200 to 400 °C, more preferably from 220 to 380 °C and most preferably
from 250 to 350 °C. The calcination time is at least 30 minutes, preferably at least 1
hour and more preferably at least 3 hours. The calcination time may be at most 12
hours, preferably at most 8 hours and more preferably at most 6 hours.
The catalysts may also contain molybdenum and/or cobalt and the method of
making the catalyst may comprise contacting the support with a sufficient amount of
molybdenum and/or cobalt. In one embodiment, an acidic impregnation solution of
nickel salt may comprise at least one molybdenum salt, for example ammonium di-
molybdate, and/or at least one cobalt salt, for example, cobalt hydroxide. The cobalt
and/or molybdenum may be present in the impregnation solution at a concentration
of from 1 to 500 g/l, preferably of from 5 to 300 g/l, and more preferably of from 10
to 280 g/l. In another embodiment, a basic impregnation solution may be used.
The catalysts may contain additional promoters and or additional catalyst
components and these may be added during one or more of the above impregnation
steps or they may be added before or after the above impregnation steps.
Catalysts prepared by these methods are typically referred to as eggshell or
eggshell type catalysts. Suitable catalysts have a metal disposition profile such that
the majority of the metal is located near the surface of the support. As described
above, the use of this type of catalyst results in a support without a significant amount
of metals on the support when it reaches a settling velocity low enough that it is
carried out of the reactor with the products and char.
The catalyst may be characterized in a number of ways, some of which will be
further described herein, but the suitable catalyst will be any catalyst that has more of
the active metal component near the surface than near the center of the support.
In one embodiment, a suitable catalyst comprises a support and at least one
active metal component wherein at least 60 wt% of the total active metal component
is located in the outer 50% of the volume of the support. The support may be
spherical, substantially spherical or any other suitable shape. The outer 50% of the
volume is the 50% of the volume of the support that is located farthest from the
middle of the catalyst. A non eggshell type catalyst would have the active metal
component evenly or substantially evenly distributed throughout the support and not
concentrated in the outer 50% of the volume of the support. In another embodiment,
the catalyst has at least 75 wt% of the active metal component in the outer 50% of the
volume of the support.
In a further embodiment, the hydropyrolysis catalyst can be viewed as being
divided into two separate regions. One region is the outer shell region, which is the
region between the surface of the catalyst and an inner boundary at a penetration
depth into the catalyst. The penetration depth is from 3 to 15 % of the catalyst
diameter. The penetration depth is the minimum depth from the surface of the
catalyst at which the average active metal concentration is within plus or minus 10%
of the active metal concentration at the geometric middle of the catalyst. The
penetration depth is preferably the depth at which the average active metal
concentration is within plus or minus 5% of the active metal concentration at the
geometric middle of the catalyst. The other region is the center region, which is the
region inside of the inner boundary at the penetration depth and which encompasses
the center of the catalyst support. The ratio of the average active metal concentration
in the outer shell region to the average active metal concentration in the center region
is in the range of from 1.3:1 to 6:1.
A catalyst as described in the above embodiment is depicted in Figure 3. The
catalyst 100 is depicted as a spherical catalyst with a center 118. The center region
116 is the region inside of penetration depth 114. The outer shell region 112 is the
region of the catalyst between the surface 110 and the penetration depth 114.
In another embodiment, the center region of the catalyst has a diameter in the
range of from 300 to 500 µm. In another embodiment, the total active metal content
of the outer shell region may be up to 30% of the total active metal content of the
catalyst.
In another embodiment, the catalyst has a center region having a diameter of
at least 200 µm and the outer shell region has a penetration depth in the range of
from 40 µm to 500 µm.
In an embodiment, a suitable hydropyrolysis catalyst comprises a support and
an active metal component where the support comprises an outer shell region and a
center region. There is optionally an intermediate region between the outer shell
region and the center region. The center region is defined as the volume of the
support within 75% of the radius of the support. The center region is preferably the
volume within 50% of the radius of the support and more preferably the volume
within 25% of the radius of the support. The outer shell region is defined as the
volume of the support between the outer surface and an inner boundary that is 25%
of the length of the radius inside of the surface. The average active metal
concentration in the outer shell region to the average active metal concentration in
the center region is from 1.3:1 to 6:1.
A catalyst as described in the above embodiment is depicted in Figure 4. The
catalyst 200 is depicted as a spherical catalyst with a center 220. The center region
204 is defined as the region inside of radius 210. The outer shell region 202 is defined
as the region between the surface 214 and the distance 212 from the surface. The
intermediate region 206 is defined as the region between the center region and the
outer shell region
During the process, char is produced. Char is the solid biomass residue
remaining after the hydropyrolysis reaction. The char is preferably entrained with the
gaseous products and carried out of the reactor. The physical characteristics of the
char determine whether it will be entrained with the gaseous products. Specifically, if
the settling velocity of the char is less than the exit bed velocity then the char will be
entrained with the gaseous products and carried out of the reactor. The char will not
necessarily be uniform as its characteristics are determined by the type of biomass,
the biomass pretreatment steps, and the hydropyrolysis reaction conditions. Further,
the char may be reduced in size by the vigorous mixing and inter-particle contact that
typify a fluidized bed.
The settling velocity of the char may be any velocity less than the exit bed
velocity, preferably less than 90% of the exit bed velocity, more preferably less than
75% of the exit bed velocity and most preferably less than 60% of the exit bed
velocity. It is understood that the individual char particles formed in the reactor may
have an initial settling velocity greater than the exit bed velocity, but that over time,
the settling velocity of the char particles may be reduced by contact with the catalyst
and other char particles until the settling velocity of the char particles is less than the
exit bed velocity.
The gaseous products will contain solid particles, such as char and catalyst
particles which are entrained with the gaseous products. These solid particles must
be removed from the gaseous products before the gaseous products are further
processed, and it is preferred for the char to be separated from the catalyst particles.
This separation can be carried out by any suitable method including settling, filters,
cyclones, or other centrifugal or centripetal separators.
In one embodiment, the gaseous products are passed through a cyclone to
remove the char and then through a filter to remove the catalyst fines. Char may be
removed by cyclone from the gaseous products stream or by way of coarse filtering. If
the char is separated by hot gas filtration, then the dust cake caught on the filters will
have to be periodically removed. It will be easier to remove because the hydrogen
produced in the hydropyrolysis reaction will have stabilized the free radicals and
saturated the olefins produced in the reaction. In conventional fast pyrolysis, the
removal of this dust cake is much more difficult because the char tends to coat the
filter and react with oxygenated pyrolysis vapors to form viscous coatings.
In an embodiment, a cyclone is first used to collect char fines from the process
vapors leaving the fluidized bed, and a porous filter is then used to collect catalyst
particles (which have a greater particle density, but a much smaller diameter than the
char). Further, two porous filters may be used in parallel, so that one may be cleaned
via backpulsing while the other is online.
Electrostatic precipitation or a virtual impactor separator may also be used to
remove char and ash particles from the hot gaseous products stream before cooling
and condensation of the pyrolysis liquid.
In another embodiment, the char may be removed by bubbling the gaseous
products stream through a recirculating liquid that is preferably the high boiling
point portion of the finished oil from the process. Char and catalyst fines may be
captured in this liquid, which can then be filtered to remove the char and catalyst
particles and/or recirculated to the hydropyrolysis reactor.
In another embodiment, large size NiMo or CoMo catalysts, deployed in an
ebullated bed, are used for char removal to provide further deoxygenation
simultaneous with the removal of fine particulates. These catalyst particles are large,
preferably from 1/8 to 1/16 inch (0.3175 to 0.1588 cm) in size so they are easily
separable from the fine char carried over from the hydropyrolysis reaction.
After removal of the char, the partially deoxygenated hydropyrolysis liquid,
together with hydrogen, carbon monoxide, carbon dioxide, water and light
hydrocarbon gases (C1-C4) from the hydropyrolysis reaction may be fed to a
hydroconversion reactor or another type of reaction zone that is used to further
process the hydropyrolysis liquid.
In a preferred embodiment, the hydroconversion reactor is operated at a
lower temperature than the hydropyrolysis reaction, in the range of from about 315
°C to about 425 °C and at about the same pressure. The liquid hourly space velocity of
this step is in the range of from about 0.3 to about 0.7. The catalyst used in this
reactor should be protected from catalyst poisons, such as sodium, potassium,
calcium, phosphorous and other metals that may be present in the biomass. The
catalyst will be protected from olefins and free radicals by the catalytic upgrading
carried out in the hydropyrolysis reactor. Catalysts typically selected for this step are
high activity hydroconversion catalysts, for example, sulfided NiMo and sulfided
CoMo catalysts. In this reaction stage, the catalyst is used to catalyze a water-gas shift
reaction of CO + H2O to make CO2 + H2, thereby enabling in-situ production of
hydrogen in the hydroconversion reactor.
Following the hydroconversion step, the liquid products will be almost
completely deoxygenated. These products can be used as a transportation fuel after
separation by means of high pressure separators and a low pressure separator by
distillation into gasoline and diesel portions. The gases exiting the hydroconversion
step are mainly carbon monoxide, carbon dioxide, methane, ethane, propane, and
butanes that can be sent to an optional steam reformer together with water to form
hydrogen to be used in the process. A portion of these gases may also be burned to
produce heat needed for the steam reformer step.
An embodiment of the hydropyrolysis reaction system 100 will be described
with respect to Figure 1. A hydropyrolysis reaction system 100 comprises a
hydropyrolysis reactor 110 that contains a bed of fluidized catalyst. Biomass is fed
into the reactor through biomass feed line 120 and hydrogen is fed into the reactor by
hydrogen feed line 122. The hydrogen and biomass react in the presence of the
catalyst and the products, including pyrolysis liquids, light gases, carbon monoxide
and char are carried out of the reactor via product line 124. The products are passed
through a cyclone 130 where the char is separated out via line 126 and the products
are removed via line 128. Other embodiments include the use of a filter and/or other
means for separating the solids from the product. Small catalyst particles may also be
carried out of the reactor via line 124 and these would be separated from the
products, either with the char or separately.
An embodiment of the hydropyrolysis reaction will be described with respect
to Figure 2. A hydropyrolysis reactor 210 contains a fluidized bed of hydropyrolysis
catalyst 230. The biomass is fed through line 220 and the hydrogen is fed through line
222. The arrows 240 depict the exit bed velocity of the gases leaving the top of the
catalyst bed. The particles 232 are either solid char particles or small catalyst
particles that are entrained with the gaseous product stream that is removed via line
224.
Examples
Example 1
Two catalysts, A and B, were prepared by impregnation as described herein.
Catalyst A was prepared by impregnating a spherical support with an acidic solution
comprising nickel, cobalt and molybdenum. The molybdenum concentration in the
solution was 160 g/l, the cobalt concentration in the solution was 50 g/l, and the
nickel concentration was 10 g/l. After impregnation, the support was dried at a
temperature of 120°C for 6 hours, and then calcined at a temperature of 350 °C for 3
hours. The once impregnated support was impregnated a second time with the acidic
solution to increase the metal content and the drying and calcining steps were
repeated. The average metal distribution across the support is shown in Figure 5. The
average metal distribution was determined using wavelength dispersive X-ray
spectrometry. The support was approximately 2000 µm in diameter, and Figure 5
shows the metal distribution of the metals across the support. As can be seen the
molybdenum is concentrated in the outer shell region of the catalyst.
Catalyst B was prepared by impregnating a spherical support with a basic
solution comprising nickel, cobalt and molybdenum. The molybdenum concentration
in the solution was 160 g/l, the cobalt concentration in the solution was 50 g/l, and
the nickel concentration was 10 g/l. After impregnation, the support was dried at a
temperature of 120 °C for 6 hours, and then calcined at a temperature of 350 °C for 3
hours. The once impregnated support was impregnated a second time with the basic
solution to increase the metal content and the drying and calcining steps were
repeated. The average metal distribution across the support is shown in Figure 6. The
average metal distribution was determined using wavelength dispersive X-ray
spectrometry. The support was approximately 2250 µm in diameter, and Figure 6
shows the metal distribution of the metals across the support. As can be seen the
molybdenum and the cobalt are concentrated in the outer shell region of the catalyst.
Example 2
This example describes the operation of a hydropyrolysis reactor using a
catalyst similar to that described above. A hydropyrolysis reactor was operated under
conditions consistent with those described above, in order to demonstrate removal of
biomass char and attrited catalyst particles from a catalyst bed via entrainment. The
hydropyrolysis reactor consisted of a tubular vessel, with an interior diameter of 3.25
cm. A catalyst bed was disposed within the reactor. Hydrogen, at a temperature of
approximately 371 °C, was fed into the bottom of the bed of catalyst in order to
fluidize it. Prior to loading, the catalyst particles were sieved, so that each particle was
small enough to pass through a sieve with a screen opening of 500 microns, but large
enough to be retained on a sieve with a screen opening of 300 microns. The reactor
was operated at 2.41 MPa and thermocouples, disposed within the fluidized bed,
indicated that the average temperature of the bed was approximately 404 °C. This
bed temperature was maintained and controlled by electric heaters. The flow rate of
hydrogen into the bottom of the bed was such that the exit velocity of vapors leaving
the bed (exit bed velocity) was 0.13 meter/second. A heated filter assembly was
disposed downstream of the fluidized-bed hydropyrolysis reactor, and was used to
trap any particles, consisting of either char or attrited catalyst, that left the fluidized
bed during the experiment. The filter was maintained at a temperature high enough
to prevent any of the vapors from condensing to form liquids in the filter assembly.
Initially, 200 grams of fresh, sulfided catalyst were disposed within the
hydropyrolysis reactor. It was established that the exit bed velocity of 0.13
meter/second was too low to remove any measurable quantity of intact catalyst
particles from the bed. The settling velocity of all the intact catalyst particles in the
bed was thus found to be larger than the exit velocity of vapors from the bed. It
should be noted that the catalyst particles were not spherical when they were loaded,
and that the settling velocity of individual particles was not determined directly. It
was established that the particles were small enough to be vigorously fluidized and
effectively mixed by the stream of fluidizing gas, but also large enough to be retained,
without being carried out by the stream of process vapors leaving the bed. No further
characterization of the aerodynamic properties of the catalyst was conducted.
The reactor was then fed a feedstock consisting of powdered hardwood. The
feedstock had a maximum particle size small enough to pass through a screen with an
opening of 250 microns. The feedstock was effectively cooled and transported in such
a manner that individual feedstock particles could not interact with each other, and
could not heat up significantly, during transport into the fluidized bed. Once the
feedstock particles arrived in the bed, they were heated very rapidly to the
temperature of the bed, via interaction with hot hydrogen, process vapors and
catalyst particles present in the bed. Each feedstock particle was rapidly devolatilized,
and the resulting vapors then had the opportunity to react with hydrogen present in
the reactor. These reactions were facilitated by the presence of the catalyst particles.
Once the feedstock particles were devolatilized, only a char particle, consisting largely
of carbon from the original feedstock, remained behind. These char particles were
significantly smaller in size than the catalyst particles in the bed, and also had a lower
particle density. As a result, these char particles were carried rapidly to the top of the
fluidized bed, and were then conveyed out of the hydropyrolysis reactor, and into the
heated filter assembly downstream of the reactor.
The system was operated over a period of three days. 2100 grams of feedstock
were loaded into the system the first day; 2100 grams of feedstock were again loaded
into the system on the second day, and 1800 grams of feedstock were loaded into the
system on the third day. After the system was shut down, 15 grams of unprocessed
feedstock were recovered. Thus, 5985 grams of feedstock were processed in the
hydropyrolysis reactor.
As described above, 200 grams of fresh catalyst were initially loaded into the
reactor. On the second day of the experiment, 17 grams of fresh catalyst were sent
into the reactor, in order to replace any catalyst that had been removed via attrition
after the first day of processing. On the third day, 17 grams of fresh catalyst were
again loaded into the reactor. When the system was shut down and unloaded, the
weight of the bed was 228 grams. The bed consisted mostly of catalyst, but also
contained some carbonaceous char material.
Since solids were recovered from the reactor and the filter assembly, an
analysis of the solids was used to confirm that the preponderance of the catalyst had
been left in the fluidized bed in the hydropyrolysis reactor, and had not been carried
out into the filter assembly. Further, the analysis confirmed that the preponderance of
the biomass char particles had been removed from the fluidized bed in the reactor,
and carried over into the filter assembly. The catalyst contained no detectible
quantities of carbon when initially loaded into the reactor. When recovered, the bed
contained 22.5% carbon, meaning that 51 grams of carbon remained in the bed. This
carbon originated in the feedstock.
The filter fines weighed 573 grams, and were 78.7% carbon. This means 451
grams of carbon were recovered from the char fines in the filter. Sizing of the particles
in the filter and the bed confirmed that the particles of the fines from the filter
assembly were in a much lower range than particles left behind in the hydropyrolysis
reactor.
Effectively, 90% of the char produced during operation of the reactor was
rapidly carried out of the fluidized bed, and accumulated in the filter assembly. The
proportion of char left behind in the reactor was related to the largest of the biomass
particles present in the feedstock. These particles would eventually have been carried
over to the filter assembly, if the fluidization in the bed had been maintained for an
extended period after cessation of feedstock addition to the bed. However, the
experiment was terminated immediately after the feedstock was used up, and there
was no opportunity to reduce the remaining char in size to a point where it would
have been carried over to the filter assembly.
The process vapors from the hydropyrolysis reactor were sent on to a second-
stage reactor after they passed through the filter assembly. In the second-stage
reactor, the process vapors were contacted with a fixed bed of catalyst, and further
hydrotreating occurred. After the experiment was over, the products were analyzed.
On a moisture and ash-free basis, 26.7% of the mass of feedstock sent into the reactor
was accounted for as gasoline-range and diesel-range hydrocarbons. The oxygen
content of the liquid hydrocarbon products was less than 1% by mass.
The bulk density of the char, collected in the filter assembly, was also assessed,
and was determined to be 0.3 g/cc. The bulk density of the catalyst in the fluidized
bed was found to be 0.9 g/cc. This difference in the bulk densities of the char and the
catalyst particles was partly responsible for the effective separation of the char from
the bed, since particles of the lower-density char could be readily carried out of the
bed, while particles of higher-density catalyst were retained.
C L A I M S
Claims (16)
- What we claim is: 5 1. A process for converting biomass to products comprising: a. contacting the biomass with hydrogen in the presence of a fluidized bed of fresh hydropyrolysis catalyst in a reactor vessel under hydropyrolysis conditions comprising a temperature in the range of from 270 °C to 450 °C and a pressure in the range of from 1 MPa to 7.5 10 MPa.; b. removing products and char from the reactor vessel; c. carrying out the contacting and removing steps for a period of time such that the fresh hydropyrolysis catalyst attrits in the fluidized bed to form small catalyst particles; and 15 d. removing at least a portion of the small catalyst particles with the products and char wherein the products leave the fluidized bed at a exit bed velocity, the char has a settling velocity that is less than the exit bed velocity, the fresh hydropyrolysis catalyst has a settling velocity that is greater than the exit 20 bed velocity, the small catalyst particles have a settling velocity that is less than the exit bed velocity and wherein the hydropyrolysis catalyst comprises a support and an active metal component wherein the catalyst is an eggshell type catalyst wherein at least 60wt% of the total active metal component is located in the outer 50% of the volume of the support. 25
- 2. A process as claimed in claim 1, wherein at least 75wt% of the total active metal component is located in the outer 50% of the volume of the support.
- 3. A process as claimed in claim 1 or claim 2 wherein the active metal component is selected from nickel, cobalt, molybdenum and mixtures thereof.
- 4. A process as claimed in any one of claims 1-3 wherein the settling velocity of 30 the char is less than 90% of the exit bed velocity.
- 5. A process as claimed in claim 4 wherein the settling velocity of the char is less than 75% of the exit bed velocity.
- 6. A process as claimed in any one of claims 1 to 5 wherein the settling velocity of the fresh hydropyrolysis catalyst is greater than 110% of the exit bed velocity.
- 7. A process as claimed in claim 6 wherein the settling velocity of the fresh hydropyrolysis catalyst is greater than 150% of the exit bed velocity. 5
- 8. A process as claimed in any one of claims 1 to 7 wherein the settling velocity of the small catalyst particles is less than 90% of the exit bed velocity.
- 9. A process as claimed in claim 8 wherein the settling velocity of the small catalyst particles is less than 75% of the exit bed velocity.
- 10. A process as claimed in any one of claims 1-9 further comprising separating 10 the products to remove the carbon monoxide and light hydrocarbons from the remainder of the products.
- 11. A process as claimed in claim 10 further comprising passing the remainder of the products to a hydroconversion reactor wherein the remainder of the products are contacted with a hydroconversion catalyst under suitable 15 hydroconversion conditions to produce a condensable liquid hydrocarbon product that has less than 1% oxygen.
- 12. A process as claimed in any one of claims 1-11 wherein the small catalyst particles are separated out by a filter and the char is separated by a cyclone.
- 13. A process as claimed in any one of claims 1-11 wherein the small catalyst 20 particles are separated out by a filter and the char is separated by a virtual impactor.
- 14. A process as claimed in any one of claims 1-11 wherein the small catalyst particles are separated out by a filter and the char is separated by an electrostatic precipitator. 25
- 15. A process as claimed in any one of claims 1-14 wherein the biomass is selected from the group consisting of plant-derived materials, including biorefinery residues and agricultural wastes, lignin, lignocellulosic biomass and aquatic biomass.
- 16. A process as claimed in any one of claims 1-14 wherein the biomass is selected 30 from the group consisting of animal and human-derived materials, including protein, fat from rendering plants, poultry wastes, sewage sludge, and wastes from aquaculture.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161559255P | 2011-11-14 | 2011-11-14 | |
US61/559,255 | 2011-11-14 | ||
PCT/US2012/064626 WO2013074437A1 (en) | 2011-11-14 | 2012-11-12 | A catalyst for producing hydrocarbons |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ624597A NZ624597A (en) | 2016-11-25 |
NZ624597B2 true NZ624597B2 (en) | 2017-02-28 |
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