CA1201080A - Process for converting biomass into hydrocarbons - Google Patents
Process for converting biomass into hydrocarbonsInfo
- Publication number
- CA1201080A CA1201080A CA000443162A CA443162A CA1201080A CA 1201080 A CA1201080 A CA 1201080A CA 000443162 A CA000443162 A CA 000443162A CA 443162 A CA443162 A CA 443162A CA 1201080 A CA1201080 A CA 1201080A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- biomass
- crystalline aluminosilicate
- aluminosilicate zeolite
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002028 Biomass Substances 0.000 title claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010457 zeolite Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- 230000003635 deoxygenating effect Effects 0.000 claims abstract description 3
- 239000002923 metal particle Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 239000010815 organic waste Substances 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 11
- 239000000446 fuel Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000013431 Pinus clausa Nutrition 0.000 description 1
- 235000000773 Pinus glabra Nutrition 0.000 description 1
- 241001502813 Pinus glabra Species 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- AUVLKSYQHWCRNS-UHFFFAOYSA-N acetylene;ethane Chemical group CC.C#C AUVLKSYQHWCRNS-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- -1 piatinum Chemical compound 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/047—Hot water or cold water extraction processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The present invention is directed to a process for converting directly biomass into hydrocarbons in one step which consists of liquefying and deoxygenating solid particles of biomass dispersed in water in presence of a catalyst system comprising a crystalline aluminosilicate zeolite containing finely divided and dispersed metal particles at conditions sufficient to obtain hydrocarbons.
The present invention is directed to a process for converting directly biomass into hydrocarbons in one step which consists of liquefying and deoxygenating solid particles of biomass dispersed in water in presence of a catalyst system comprising a crystalline aluminosilicate zeolite containing finely divided and dispersed metal particles at conditions sufficient to obtain hydrocarbons.
Description
The present invention relates to a process for - producing hydrocarbon fuels from renewable biomass, and more particularly, to those processes in which biomass material can be converted directly)> into an oil by heating small biomass particles with water, catalysts and reducing agents to temperatures up to 350C.
It is known that biomass can be thermochemically converted to liquid fuels by two main routes. The route No.
1 is called Indirect liquefaction, i.e., thermal gasification inducing conversion of biomass to a mixture of gas, liquids and tars by pyrolysis followed by catalytic liquefaction of the products. The route No. 2 is called Direct lique-faction, i.e. conversion in one step biomass to an oil by heating biomass particles in water in presence of reducing agents and catalysts to temperature up to 350.
The advantage of indirect liquefaction (vs direct) is minimization of oxygenated compounds in the liquid hydro-carbon fuel product as teached by US patent Nos. 4,320,241 and 4,308,411 to Frankiewicz by use of catalysts and the disadvantages are the low conversion yield, the low energy conversion efficiency, the need of two-step processes (gasification and liquefaction) requiring more complex process design and higher costs. Direct liquefaction provides a very high overall energy conversion efficiency and a conversion yield of about 35~ the weight of the feed. The heavy oil obtained with up to 20~ oxygen content and with a heating value of 1450-1500 Btu/lb may be upgraded by distillation or by hydrogenation which would convert phenol to aromatic hydrocarbons.
It is desirable to develop procedures by which the yields and the quality of the liquid fuels can be upgraded in one step during the conversion to permit their immediate use as it without costly refining or upgrading.
The present invention therefore provides a ,,~.
lZ01080 procedure for obtaining a higher yield and quality liquid fuel from the direct liquefaction process.
The invention relates to a process for converting directly biomass into hydrocarbons in one step which consists of liquefying and deoxygenating solid particles of biomass dispersed in water in presence of a catalyst system comprising - a crystalline aluminosilicate zeolite containing finely divided and dispersed metal particles at conditions sufficient to obtain hydrocarbons~
The present invention relates to a process for producing hydrocarbon fuels from renewable biomass. Examples of biomass are spruce pine and poplar residues. The invented process is not limited to these examples and can be applied to any biomass materials such as agricultural residues and urban refuse, and land- and water-based plant material such as trees, grasses and alguae. Such a biomass is preferably of a particle size above 0.350 mm and is dispersed in water in percentage ratio of 10 to 30.
The subject invention is directed to a process for the thermal conversion of biomass at about 280C to about 350C in presence of water and a catalyst system, wherein increased yields of liquid and gaseous hydrocarbons produced can be used as fuels and as feedstocks for chemical manufacture.
The excess char is removed to serve as fuel.
The process according to the subject invention is conducted in an inert or reducing atmosphere.
It has been observed that the residence time has an effect upon the yields and quality of hydrocarbon liquids. Shorter residence times would increase liquid production. Suitable residence times are about 2 to about 5 minutes in the conversion zone operated at the mean temperature of 320C. Higher residence time leads to lower yields due to secondary reactions such as polymerisation and tar formation. The Applicant has found that hydrocarbon ~2Q~(~80 liquid fuel yield and quality be further increased, while maintaining high overall process efficiency by using specific catalysts.
These catalysts are generally described as crystal-line aluminosilicate zeolite minerals having SiO2/A1203 ratiohigher than 4 and a pore size of about 4.0 to about 8.OA.
Such zeolites may be for example H-Y zeolite, ZSM-5 and H-mordenite. These zeolites are described in detail in US
Patent No. 3,702,886 and from S.A. Rabo (Zeolite chemistry and catalyst, ACS 1975) and do not constitute part of this invention.
The Applicant has also found that mono and poly-metallic particles finely dispersed and deposited in the zeolites enhance considerably the deoxygenation rate and the water shift reaction. Metals are dispersed in the pores and cavities as cations by well known techniques in the art such as ion exchange technique and are reduced under hydrogen at about 400C. Metals used are selected among iron, nickel, palladium, piatinum, cobalt, molybdenum, chromium, titanium, copper, ruthenium and zinc. The content of metals in zeolites is from 1 to 10%.
It is well known in the art that the first step in a direct liquefaction process is a thermal depolymerisation of carbohydrate polymer (cellulose, hemicellulose) and phenolic polymer (lignin) followed by deoxygenation reaction, to give liquid fuels; and that the depolymerisation products are potent precursor for coke formation, the shape selective>~
zeolites are not themselves capable of efficient deoxygenation even in water medium in presence of steam. The Applicant has found that an inert and thermall~ stable support has a marked eEfect on the rate of coke formation besides the residence time process parameter. The dilution of active zeolite catalysts with a support having a surface area higher than 0.5 m2g-1 such as alumina, abestos and synthetic silica-, ~
alumina yields a composite having ~low coking tendencies andenhances activity for converting oxygenated depolymerized products of biomass to hydrocarbons. Methods for preparing admixture of zeolite catalysts dispersed in a solid support with a binder are well known in the art. The ratio of zeolite to support may vary from 0.01 to 0.30. Supports are selected based on their thermal stability. Silica must be avoided because of its volatility in steam at high tempe-rature.
In a preferred embodiment, the catalytic liquefaction process of this invention may be carried out in the presence of hydrogen, carbon monoxide or a suitable inert gas e.g.
nitrogen or argon at temperature of 280 to 350C and pressure of 1300 to 3000 psi with residence time of 2 to 5 minutes. Water is used as solvent.
In order to better understand the invention without limiting the same, reference is made to the accompanying drawing which is a schematic illustration of the invention according to which the biomass is thermally converted to liquids composed of aliphatic, aromatic, olefine and function-alized compounds containing oxygen and nitrogen, and gases such as methane and ethane acetylene. The thermal conversion zone consists of a high pressure vessel equipped with a rotating stirred basket holding the catalysts. Low residence time of the product in the thermal conversion zone is obtained by ejecting the reaction mixture to a let-down water cooling vessel. Residence time in the thermal conversion zone is from 0.2 minute to any time. The quenching time from 350C
to 90C is 1.5 minutes.
Referring to the appended diagram, the plant biomass is ground to flour of 0.350 mm size and mixed with water to obtain a slurry of 10 to 30 percent by weight. The slurry is heated to 70C and fed to a reactor feeder system. The reactor zone is flushed with nitrogen and heated to about 400C to 450C. The catalyst basket is rotated to 500 rpm and the slurry is injected rapidly~(about 10 sec) in the conversion zone by a water piston at 200 psi. The reactional mixture reaches 300 to 350C and developes 1000 to 3000 psi in less than 1 minute. The product can then be ejected out of the conversion zone by a water cooled valve to a let-down water-cooled vessel. Steam is then injected to the reactor zone to remove solid tar formed in the catalyst basket. The product oil is extracted with dichloromethane, the water layer containing less than 5% of organic products is mixed - with fresh waste and recycled.
.. , . ...... . . . .. . . ... ~
It is known that biomass can be thermochemically converted to liquid fuels by two main routes. The route No.
1 is called Indirect liquefaction, i.e., thermal gasification inducing conversion of biomass to a mixture of gas, liquids and tars by pyrolysis followed by catalytic liquefaction of the products. The route No. 2 is called Direct lique-faction, i.e. conversion in one step biomass to an oil by heating biomass particles in water in presence of reducing agents and catalysts to temperature up to 350.
The advantage of indirect liquefaction (vs direct) is minimization of oxygenated compounds in the liquid hydro-carbon fuel product as teached by US patent Nos. 4,320,241 and 4,308,411 to Frankiewicz by use of catalysts and the disadvantages are the low conversion yield, the low energy conversion efficiency, the need of two-step processes (gasification and liquefaction) requiring more complex process design and higher costs. Direct liquefaction provides a very high overall energy conversion efficiency and a conversion yield of about 35~ the weight of the feed. The heavy oil obtained with up to 20~ oxygen content and with a heating value of 1450-1500 Btu/lb may be upgraded by distillation or by hydrogenation which would convert phenol to aromatic hydrocarbons.
It is desirable to develop procedures by which the yields and the quality of the liquid fuels can be upgraded in one step during the conversion to permit their immediate use as it without costly refining or upgrading.
The present invention therefore provides a ,,~.
lZ01080 procedure for obtaining a higher yield and quality liquid fuel from the direct liquefaction process.
The invention relates to a process for converting directly biomass into hydrocarbons in one step which consists of liquefying and deoxygenating solid particles of biomass dispersed in water in presence of a catalyst system comprising - a crystalline aluminosilicate zeolite containing finely divided and dispersed metal particles at conditions sufficient to obtain hydrocarbons~
The present invention relates to a process for producing hydrocarbon fuels from renewable biomass. Examples of biomass are spruce pine and poplar residues. The invented process is not limited to these examples and can be applied to any biomass materials such as agricultural residues and urban refuse, and land- and water-based plant material such as trees, grasses and alguae. Such a biomass is preferably of a particle size above 0.350 mm and is dispersed in water in percentage ratio of 10 to 30.
The subject invention is directed to a process for the thermal conversion of biomass at about 280C to about 350C in presence of water and a catalyst system, wherein increased yields of liquid and gaseous hydrocarbons produced can be used as fuels and as feedstocks for chemical manufacture.
The excess char is removed to serve as fuel.
The process according to the subject invention is conducted in an inert or reducing atmosphere.
It has been observed that the residence time has an effect upon the yields and quality of hydrocarbon liquids. Shorter residence times would increase liquid production. Suitable residence times are about 2 to about 5 minutes in the conversion zone operated at the mean temperature of 320C. Higher residence time leads to lower yields due to secondary reactions such as polymerisation and tar formation. The Applicant has found that hydrocarbon ~2Q~(~80 liquid fuel yield and quality be further increased, while maintaining high overall process efficiency by using specific catalysts.
These catalysts are generally described as crystal-line aluminosilicate zeolite minerals having SiO2/A1203 ratiohigher than 4 and a pore size of about 4.0 to about 8.OA.
Such zeolites may be for example H-Y zeolite, ZSM-5 and H-mordenite. These zeolites are described in detail in US
Patent No. 3,702,886 and from S.A. Rabo (Zeolite chemistry and catalyst, ACS 1975) and do not constitute part of this invention.
The Applicant has also found that mono and poly-metallic particles finely dispersed and deposited in the zeolites enhance considerably the deoxygenation rate and the water shift reaction. Metals are dispersed in the pores and cavities as cations by well known techniques in the art such as ion exchange technique and are reduced under hydrogen at about 400C. Metals used are selected among iron, nickel, palladium, piatinum, cobalt, molybdenum, chromium, titanium, copper, ruthenium and zinc. The content of metals in zeolites is from 1 to 10%.
It is well known in the art that the first step in a direct liquefaction process is a thermal depolymerisation of carbohydrate polymer (cellulose, hemicellulose) and phenolic polymer (lignin) followed by deoxygenation reaction, to give liquid fuels; and that the depolymerisation products are potent precursor for coke formation, the shape selective>~
zeolites are not themselves capable of efficient deoxygenation even in water medium in presence of steam. The Applicant has found that an inert and thermall~ stable support has a marked eEfect on the rate of coke formation besides the residence time process parameter. The dilution of active zeolite catalysts with a support having a surface area higher than 0.5 m2g-1 such as alumina, abestos and synthetic silica-, ~
alumina yields a composite having ~low coking tendencies andenhances activity for converting oxygenated depolymerized products of biomass to hydrocarbons. Methods for preparing admixture of zeolite catalysts dispersed in a solid support with a binder are well known in the art. The ratio of zeolite to support may vary from 0.01 to 0.30. Supports are selected based on their thermal stability. Silica must be avoided because of its volatility in steam at high tempe-rature.
In a preferred embodiment, the catalytic liquefaction process of this invention may be carried out in the presence of hydrogen, carbon monoxide or a suitable inert gas e.g.
nitrogen or argon at temperature of 280 to 350C and pressure of 1300 to 3000 psi with residence time of 2 to 5 minutes. Water is used as solvent.
In order to better understand the invention without limiting the same, reference is made to the accompanying drawing which is a schematic illustration of the invention according to which the biomass is thermally converted to liquids composed of aliphatic, aromatic, olefine and function-alized compounds containing oxygen and nitrogen, and gases such as methane and ethane acetylene. The thermal conversion zone consists of a high pressure vessel equipped with a rotating stirred basket holding the catalysts. Low residence time of the product in the thermal conversion zone is obtained by ejecting the reaction mixture to a let-down water cooling vessel. Residence time in the thermal conversion zone is from 0.2 minute to any time. The quenching time from 350C
to 90C is 1.5 minutes.
Referring to the appended diagram, the plant biomass is ground to flour of 0.350 mm size and mixed with water to obtain a slurry of 10 to 30 percent by weight. The slurry is heated to 70C and fed to a reactor feeder system. The reactor zone is flushed with nitrogen and heated to about 400C to 450C. The catalyst basket is rotated to 500 rpm and the slurry is injected rapidly~(about 10 sec) in the conversion zone by a water piston at 200 psi. The reactional mixture reaches 300 to 350C and developes 1000 to 3000 psi in less than 1 minute. The product can then be ejected out of the conversion zone by a water cooled valve to a let-down water-cooled vessel. Steam is then injected to the reactor zone to remove solid tar formed in the catalyst basket. The product oil is extracted with dichloromethane, the water layer containing less than 5% of organic products is mixed - with fresh waste and recycled.
.. , . ...... . . . .. . . ... ~
Claims (17)
1. A process for converting directly biomass into hydrocarbons in one step which consists of liquefying and deoxygenating solid particles of biomass dispersed in water in presence of a catalyst system comprising a crystalline aluminosilicate zeolite containing finely divided and dispersed metal particles at conditions sufficient to obtain hydrocarbons.
2. Process according to claim 1, wherein said biomass is defined as organic waste, agricultural residues, urban refuse, and land-and water-based plant material.
3. Process according to claim 1, wherein said biomass is of a particle size above 0.350 mm.
4. Process according to claim 1, wherein said biomass is dispersed in water in percentage ratio of 10 to 30.
5. Process according to claim 1, wherein the process is conducted at a temperature of about 280°C to about 350°C.
6. Process according to claim 1, wherein the process is conducted at a pressure of about 1000 psi to about 3000 psi.
7. Process according to claim 1, wherein the process is conducted in an inert or reducing atmosphere.
8. Process according to claim 1, wherein the residence time of said biomass material in contact with said catalyst ranges from 2 to about 5 minutes.
9. Process according to claim 1, wherein said catalyst system is contained in a rotating stirred basket.
10. Process according to claim 1, wherein said catalyst includes a porous support materials in admixture with said crystalline aluminosilicate zeolite.
11. Process according to claim 10, wherein said porous support materials are selected among alumina, abestos and synthetic silica-alumina.
12. Process according to claim 10 or 11, wherein said support materials have a surface area higher than 0.5 m2g-1.
13. Process according to claim 10, wherein said crystalline aluminosilicate zeolite has a pore size of about 4.0 to about 8ØANG..
14. Process according to claim 13 wherein said crystalline aluminosilicate zeolite has a silica to alumina molar ratio higher than 4.
15. Process according to claim 14, wherein said crystalline aluminosilicate zeolite contains disperse metals in pores and cavities.
16. Process according to claim 15, wherein said metals are selected from the group consisting of iron, nickel, palladium, platinum, cobalt, molybdenum, chromium, titanium, copper, ruthenium and zinc.
17. Process according to claim 1, wherein said crystalline aluminosilicate zeolite is selected from the group consisting of H - Y zeolite, ZSM-5 and H-mordenite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000443162A CA1201080A (en) | 1983-12-13 | 1983-12-13 | Process for converting biomass into hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000443162A CA1201080A (en) | 1983-12-13 | 1983-12-13 | Process for converting biomass into hydrocarbons |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1201080A true CA1201080A (en) | 1986-02-25 |
Family
ID=4126739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000443162A Expired CA1201080A (en) | 1983-12-13 | 1983-12-13 | Process for converting biomass into hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1201080A (en) |
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| EP1268717A4 (en) * | 2000-03-23 | 2004-03-17 | Univ West Virginia | METHOD FOR CONVERTING AN AGRICULTURAL WASTE INTO A LIQUID FUEL, AND ASSOCIATED DEVICE |
| EP1889870A1 (en) * | 2006-08-16 | 2008-02-20 | BIOeCON International Holding N.V. | Stable suspensions of biomass comprising inorganic particulates |
| WO2008109877A1 (en) * | 2007-03-08 | 2008-09-12 | Virent Energy Systems, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
| WO2008009643A3 (en) * | 2006-07-17 | 2009-04-23 | Bioecon Int Holding Nv | Catalytic pyrolysis of fine particulate biomass, and method for reducing the particle size of solid biomass particles |
| EP2071005A1 (en) * | 2007-12-03 | 2009-06-17 | BIOeCON International Holding N.V. | Process for the selective de-oxygenation of biomass |
| WO2009071541A3 (en) * | 2007-12-03 | 2009-07-23 | Bioecon Int Holding Nv | Process for making bio-oils and fresh water from aquatic biomass |
| US20110144396A1 (en) * | 2009-12-15 | 2011-06-16 | Conocophillips Company | Process for converting biomass to hydrocarbons and oxygenates |
| US8231857B2 (en) | 2005-12-21 | 2012-07-31 | Virent, Inc. | Catalysts and methods for reforming oxygenated compounds |
| US8350108B2 (en) | 2008-08-27 | 2013-01-08 | Virent, Inc. | Synthesis of liquid fuels from biomass |
| RU2472840C2 (en) * | 2007-03-08 | 2013-01-20 | Вайрент, Инк. | Synthesis of liquid fuel and chemical agents from oxygen-containing hydrocarbons |
| US8366907B2 (en) | 2010-08-02 | 2013-02-05 | Battelle Memorial Institute | Deoxygenation of fatty acids for preparation of hydrocarbons |
| US8834587B2 (en) | 2006-12-20 | 2014-09-16 | Virent, Inc. | Method of producing gaseous products using a downflow reactor |
| US9085735B2 (en) | 2013-01-02 | 2015-07-21 | American Fuel Producers, LLC | Methods for producing synthetic fuel |
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1983
- 1983-12-13 CA CA000443162A patent/CA1201080A/en not_active Expired
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1268717A4 (en) * | 2000-03-23 | 2004-03-17 | Univ West Virginia | METHOD FOR CONVERTING AN AGRICULTURAL WASTE INTO A LIQUID FUEL, AND ASSOCIATED DEVICE |
| US8231857B2 (en) | 2005-12-21 | 2012-07-31 | Virent, Inc. | Catalysts and methods for reforming oxygenated compounds |
| WO2008009643A3 (en) * | 2006-07-17 | 2009-04-23 | Bioecon Int Holding Nv | Catalytic pyrolysis of fine particulate biomass, and method for reducing the particle size of solid biomass particles |
| EP1889870A1 (en) * | 2006-08-16 | 2008-02-20 | BIOeCON International Holding N.V. | Stable suspensions of biomass comprising inorganic particulates |
| WO2008020046A3 (en) * | 2006-08-16 | 2008-07-17 | Bioecon Int Holding Nv | Stable suspensions of biomass comprising inorganic particulates |
| US8808408B2 (en) * | 2006-08-16 | 2014-08-19 | Kior, Inc. | Stable suspensions of biomass comprising inorganic particulates |
| US8715377B2 (en) * | 2006-08-16 | 2014-05-06 | Kior, Inc. | Stable suspensions of biomass comprising inorganic particulates |
| US20100275507A1 (en) * | 2006-08-16 | 2010-11-04 | Bioecon International Holding N.V. | Stable suspensions of biomass comprising inorganic particulates |
| US20130000182A1 (en) * | 2006-08-16 | 2013-01-03 | Kior Inc. | Stable suspensions of biomass comprising inorganic particulates |
| US8834587B2 (en) | 2006-12-20 | 2014-09-16 | Virent, Inc. | Method of producing gaseous products using a downflow reactor |
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| US8933281B2 (en) | 2007-03-08 | 2015-01-13 | Virent, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
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| WO2009071541A3 (en) * | 2007-12-03 | 2009-07-23 | Bioecon Int Holding Nv | Process for making bio-oils and fresh water from aquatic biomass |
| EP2071005A1 (en) * | 2007-12-03 | 2009-06-17 | BIOeCON International Holding N.V. | Process for the selective de-oxygenation of biomass |
| US20100294643A1 (en) * | 2007-12-03 | 2010-11-25 | Kior Inc. | Process for the selective de-oxygenation of biomass |
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| US20110144396A1 (en) * | 2009-12-15 | 2011-06-16 | Conocophillips Company | Process for converting biomass to hydrocarbons and oxygenates |
| US8846992B2 (en) * | 2009-12-15 | 2014-09-30 | Philips 66 Company | Process for converting biomass to hydrocarbons and oxygenates |
| US8882990B2 (en) | 2010-08-02 | 2014-11-11 | Battelle Memorial Institute | Deoxygenation of fatty acids for preparation of hydrocarbons |
| US8388829B2 (en) | 2010-08-02 | 2013-03-05 | Battelle Memorial Institute | Deoxygenation of fatty acids for preparation of hydrocarbons |
| US8366907B2 (en) | 2010-08-02 | 2013-02-05 | Battelle Memorial Institute | Deoxygenation of fatty acids for preparation of hydrocarbons |
| US9085735B2 (en) | 2013-01-02 | 2015-07-21 | American Fuel Producers, LLC | Methods for producing synthetic fuel |
| US10118159B2 (en) | 2013-09-06 | 2018-11-06 | Reliance Industries Limited | Catalyst composition and a catalytic process for conversion of biomass to crude bio oil |
| US10391474B2 (en) | 2013-09-06 | 2019-08-27 | Reliance Industries Limited | Process for preparation of hydrocarbon fuel from waste rubber |
| EP3685917A1 (en) | 2013-09-06 | 2020-07-29 | Reliance Industries Limited | A catalyst composition and a catalytic process for conversion of biomass to crude bio oil |
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