CN102441433B - Ion liquid catalyst and method for liquefying and gasifying catalytic biomass waste thereof - Google Patents
Ion liquid catalyst and method for liquefying and gasifying catalytic biomass waste thereof Download PDFInfo
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- CN102441433B CN102441433B CN201110268571.XA CN201110268571A CN102441433B CN 102441433 B CN102441433 B CN 102441433B CN 201110268571 A CN201110268571 A CN 201110268571A CN 102441433 B CN102441433 B CN 102441433B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 239000002028 Biomass Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 title abstract description 20
- 239000002699 waste material Substances 0.000 title abstract description 6
- 230000003197 catalytic effect Effects 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000012216 screening Methods 0.000 claims abstract description 3
- 239000002608 ionic liquid Substances 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- NKRASMXHSQKLHA-UHFFFAOYSA-M 1-hexyl-3-methylimidazolium chloride Chemical compound [Cl-].CCCCCCN1C=C[N+](C)=C1 NKRASMXHSQKLHA-UHFFFAOYSA-M 0.000 claims description 7
- 239000011831 acidic ionic liquid Substances 0.000 claims description 7
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 claims description 6
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 238000000703 high-speed centrifugation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 25
- 150000003839 salts Chemical class 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005057 refrigeration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000012075 bio-oil Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001722 flash pyrolysis Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010921 garden waste Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a method for liquefying and gasifying catalytic biomass waste of the ion liquid catalyst, comprising the following steps of: after ion liquid and metal salt are prepared into a catalyst at certain ratio, drying, smashing and screening biomass waste to obtain particle powder of which the particle diameter is 10-60 meshes; mixing the particle powder with the catalyst; emptying air in a reactor for pyrolysis reaction; cooling a pyrolysis product by a refrigeration plant and collecting the pyrolysis product; and recovering and recycling the catalyst. The catalyst used by the method has the advantages of high activity and good stability, can be recycled, is practical and is convenient to operate, and cost is lowered, the biomass waste can be converted into the liquid-phase or gas-phase low-molecule pyrolysis product in a directed mode, and a new path is opened up for low-cost recycling of the biomass waste.
Description
Technical field
A kind of method that the present invention relates to ionic liquid catalyst and catalysis biomass discarded object liquefaction gasification thereof, belongs to biomass as resources field.
Background technology
Since the industrial revolution, along with human economy fast development, people are very high to fossil fuel use amount and degree of dependence, however these fossil energies not only reserves be limited, and a large amount of burnings can bring series of environmental problems.In the face of the day by day exhausted severe situation of existing fossil energy, find novel renewable energy and become the eager problem solving of people.Biomass energy is the fourth-largest energy that is only second to coal, oil, natural gas, and increasing country payes attention to it and develop and uses, and makes it in following new energy resources system, occupy potential strategic position.China is a large agricultural country, and Biomass Energy Resources is abundant, and only agricultural crop straw just can be produced up to 600,000,000 tons every year, has great importance to alleviating the energy availability and demand pressure of China and serious environmental problem if be translated into fuel oil and the combustion gas of high added value.
In the last few years, it is very fast that stalk pyrolytic technique developed, and mainly concentrates on slow pyrolysis, conventional pyrolysis and three kinds of technology of flash pyrolysis, and the form of the corresponding thermal decomposition product of each technology has very big difference, and for example flash pyrolysis is mainly to produce oil as main.But three kinds of pyrolytic techniques all need carry out under hot conditions, and the oil producing can not directly use, and must after follow-up refining, can use, and makes the application cost of biomass pyrolytic produce oil high.How taking effective measures the quality and the quality that improve produce oil, reduce the energy consumption of pyrolysis, is the focus of current biomass energy research.For example in cracking process, add some slaine (MgCl
2, CaCl
2, KCl, NaCl, CaO, ZnCl
2deng) as catalyst, make pyrolysis towards low little molecule (as glycollic aldehyde, acids etc.) liquid products conversion or carry out towards gasification aspect.But these add the method for catalyst, exist catalyst be difficult to from the predicament effectively separating pyrolysis residue, the catalyst of the general pyrolysis participating in is all disposable expendable substantially, makes catalyse pyrolysis cost very high.
Ionic liquid is a kind of organic fuse salt being at room temperature in a liquid state, there is outstanding heat endurance and chemical stability, almost negligible vapour pressure, wider electrochemical window and liquid range, can regulate its physicochemical properties by different cations and anion.Much research shows, some ionic liquid are interior and intermolecular hydrogen bonding by cellulosic molecule in destruction stalk, makes it have good solvability to cellulose.Adopt the carrier of ionic liquid as stalk pyrolysis catalysts, both can promote that stalk pyrolysis temperature decreased, thermal decomposition product tends to little molecularization, and the catalyst that can make again pyrolysis add is well reclaimed.
Patent CN101402658A(publication number) announce using ionic liquid as solvent, acidic molecular sieves etc. are catalyst, at 100～300 DEG C of pressure 0.01～4.0MPa and temperature, carry out the reaction of homogeneous catalysis thermal degradation of cellulose, after reaction time 20～60min, can obtain cellulosic catabolite, ionic liquid and catalyst be recyclable recycling all.But in this patent, play the solid acid molecular sieve of catalytic action, after pyrolytic reaction completes, the residue powder that the space of molecular sieve is easily produced by pyrolysis stops up, and causes molecular sieve catalytic active to reduce, and in use molecular sieve mixes mutually with cracked residue, reclaim more difficult.
Patent CN 101085924A (publication number) announced a kind of taking " high temperature ironic liquid " as carrier, technique and the device of dissolving and catalyst biomass pyrolytic.The description of this patent system pyrolysis installation and technological process, advantage is mainly that biological particles mixes with high temperature ironic liquid, temperature field is stable, pyrolysis is rapid, device structure is simple and practical.But " high temperature ironic liquid " mentioned in patent is to belong to high-temperature fusion salt, is all inorganic salts substantially, and molten point is quite high, not very ionic liquid truly, after still existing pyrolysis and completing, catalyst is difficult to situation about recycling.
Summary of the invention
The present invention is directed to some problems that existing biomass pyrolytic technology exists, object is to provide a kind of ionic liquid catalyst, ionic liquid catalyst is made up of a kind of ionic liquid and one or both slaines or alkali, wherein ionic liquid and slaine ratio are mol ratio 1:0.05～3, and the molar ratio of ionic liquid and metal base is 1:0.05～2.
Intermediate ion liquid of the present invention is acidic ionic liquid or slaine had compared with the one in the ionic liquid of high-solvency, and wherein acidic ionic liquid is [HS0
3-bpy] CF
3s0
3, [HSO
3-bvim] HSO
3, [HSO
3-b-N (CH
3)
3] HSO
3,
；
Having compared with the ionic liquid of high-solvency to slaine is chlorination 1-butyl-3-methylimidazole salt ([bmim] Cl), 1-butyl-3-methylimidazolium bromide salt ([bmim] Br), [emim] Cl, [hmim] Cl
、
，
、。
In the present invention, slaine or alkali are FeCl
3, NiCl
2, ZnCl
2, FeCl
2, MgCl
2, AlCl
3, KOH, NaOH, Ca (OH)
2in a kind of or two kinds.
Another object of the present invention is to provide a kind of method of ionic liquid catalyst catalysis biomass discarded object liquefaction gasification, this is the method that biomass castoff thermal decomposition product is tended to little molecularization, and make the catalyst that participates in reaction be easy to separate from cracked residue, reactant recovery is easy, for biomass castoff low cost resource has been opened up a new way.The invention provides a kind of practicality, simple to operate, reactivity and the high biomass conversion technology of conversion ratio.
The present invention mainly processes the biomass castoffs such as the livestock waste of garden wastes, agricultural crop straw and high wood fibre content, as catalyst, thermal decomposition product is carried out towards little molecularization its catalyst at ionic liquid and slaine composition.
It is as follows that intermediate ion liquid catalyst of the present invention is prepared required raw material:
1. ionic liquid
1) acidic ionic liquid is [HS0
3-bpy] CF
3s0
3, [HSO
3-bvim] HSO
3, [HSO
3-b-N (CH
3)
3] HSO
3;
2) slaine is had to the ionic liquid compared with high-solvency
Chlorination 1-butyl-3-methylimidazole salt ([bmim] Cl), 1-butyl-3-methylimidazolium bromide salt ([bmim] Br), [emim] Cl, [hmim] Cl
，?
，
2. slaine and alkali: FeCl
3, NiCl
2, ZnCl
2, FeCl
2, MgCl
2, AlCl
3, KOH, NaOH, Ca (OH)
2.
The structure principle of intermediate ion liquid catalyst of the present invention
As required, select ionic liquid and slaine or alkali kind, for example, when product need to carry out towards liquid phase is degraded, select KOH, Ca (OH)
2mix composition ionic liquid catalyst with acidic ionic liquid in 1:0.05～2 ratio, make pyrolysis meeting towards low little molecule (as glycollic aldehyde, acids etc.) liquid products conversion; Thermal decomposition product, towards gas phase is degraded while carrying out, can be selected Fe
3+and/or Ni
3+slaine and the strong ionic liquid of its solvability is formed to the ionic liquid catalyst of similar complex in 1:0.05～3 ratio, in the product that can make, bio oil productive rate obviously declines, gaseous state productive rate significantly increases, especially H in gaseous state
2and CO
2productive rate increase.
The present invention carries out as follows:
(1) preparation of ionic liquid catalyst
Need to change into the difference of liquid phase or the low molecular heat hydrolysis products of gas phase according to biomass castoff, from ionic liquid and slaine or alkali, select a kind of ionic liquid and one or both slaines or alkali to be hybridly prepared into by a certain percentage ionic liquid catalyst;
(2) particle diameter biomass castoff drying, pulverizing, screening being made after processing is that 10～60 object particle powders mix mutually with catalyst, biomass castoff powder is after the ratio of 1:0.03～15 is mixed by weight percentage with catalyst, mixture is positioned in reactor, before pyrolytic reaction, pass into the air in nitrogen purge reactor, carry out under oxygen free condition to ensure reaction, heat temperature raising, temperature is controlled in 160～300 DEG C of temperature ranges, and the reaction time is 10～50 minutes;
(3) gaseous mixture producing in pyrolytic reaction is cooling by condensing unit, obtain condensed fluid bio oil and gas, the residue in reactor adds a small amount of water, after high speed centrifugation, remove residue, the ionic liquid catalyst aqueous solution after dewatering, recyclable recycling.
Intermediate ion liquid of the present invention and slaine in molar ratio 1:0.05～3 mix, and ionic liquid and metal base in molar ratio 1:0.05～2 are mixed.
When in the present invention, slaine or alkali are two kinds, they are mixed to form mixed liquor in 1:0.05～2 in molar ratio.
When in the present invention, thermal decomposition product is liquid phase lower-molecular substance, ionic liquid catalyst is a kind of acidic ionic liquid and KOH, Ca (OH)
2mixed liquor mixes the K that contains of composition in 1:0.05～2 ratio
+, Ca
2+ionic liquid catalyst.
When in the present invention, thermal decomposition product is gas phase lower-molecular substance, ionic liquid catalyst is a kind of slaine to be had compared with the ionic liquid of high-solvency and Fe
3+and/or Ni
3+the catalyst that is mixed to form in 1:0.05～3 ratio of slaine.
The present invention compared with prior art has advantages of as follows:
1. high, the good stability of catalyst activity of the present invention, making are simple, and pyrolysis reaction temperature is low, thermal decomposition product composition can regulate and control by the formation that changes catalyst, and the follow-up refining of product liquid obtaining and processing are relative simple;
2. the constructed clear and definite proposition thermal decomposition product of catalyst of the present invention tends to little molecularization, compared with traditional pyrolytic technique, object product composition is more simple and clear and definite, catalyst can be recycled, reduce purification cost, for a new way has been opened up in large-scale industrial production and the utilization of living beings.
Brief description of the drawings
Fig. 1 is process flow diagram of the present invention.
Detailed description of the invention
Embodiment 1:
Technical process and step in the present embodiment are as follows:
1. getting particle diameter is 50 object biomass castoffs----stalk butt 5g mixes with ionic liquid catalyst, and ionic liquid catalyst is by [HS0
3-bpy] CF
3s0
3(alkali is by KOH and Ca (OH) with aqueous slkali
2composition, mol ratio is 1:0.05) in molar ratio 1:0.05 be mixed with, be placed in stainless steel reactor; Butt mixes for the ratio of 1:5 by weight percentage with ionic liquid catalyst, adds catalyst 25g; Closed reactor, passes into nitrogen, discharges remaining air in reactor; Open heater, controlling reaction temperature is 250 DEG C, and the reacting gas product of generation is through condensing unit condensation and collect respectively condensate liquid and cooled gaseous product.
2. pyrolytic reaction proceeds to 50 minutes, substantially without gaseous product when discharging in reactor, stop heating.
3. the condensed fluid of collecting is distilled, obtain the lighter bio oil of color.
4. the material after pyrolysis, adds a small amount of water, and high speed centrifugation liquid is removed the residue that reaction produces, and obtains aqueous catalyst solution, removes after moisture, and catalyst can be recycled.
Embodiment 2:
Technical process in the present embodiment and step are identical with embodiment 1, and different is that ionic liquid catalyst is by [HS0
3-bpy] CF
3s0
3(alkali is by NaOH and Ca (OH) with alkali
2composition, mol ratio is 1:1) in molar ratio 1:1 be mixed with, reaction temperature is controlled at 260 DEG C, finally obtains the lighter bio oil of color.
Embodiment 3:
Technical process in the present embodiment and step are identical with embodiment 1, and different is that ionic liquid catalyst is by [bmim] Cl and FeCl
3-NiCl
2mixed liquor is the formulated (FeCl of 1:2 in molar ratio
3and NiCl
21:2 mixes in molar ratio), reaction temperature is controlled at 180 DEG C, finally obtains more gaseous products, and gaseous products is to be mainly H
2, CO, CH
4, CO
2.
Embodiment 4:
1. getting particle diameter is 60 object biomass castoff-----stalk butt 12g and [bmim] Cl/ZnCl
2-FeCl
2composition from
Sub-liquid catalyst mixes ([hmim] Cl, ZnCl
2and FeCl
2three's mol ratio is 1:1:0.05), be placed in quartz reactor; The weight proportion of butt and catalyst is 1:2, adds catalyst 24g; Closed reactor, passes into nitrogen, discharges remaining air in reactor; Quartz reactor is positioned in the microwave of 2450 megahertzes, opens microwave heating equipment, it is 200 DEG C that pyrolysis reaction temperature is made as, and the reacting gas product of generation is through condensing unit condensation and collect respectively condensate liquid and cooled gaseous product.
2. pyrolytic reaction proceeds to 10 minutes, substantially without gaseous product when discharging in reactor, stop heating.
3. the condensed fluid of collecting is distilled, obtain the bio oil of higher yields.
4. the material after pyrolysis, adds a small amount of water, and high speed centrifugation liquid is removed the residue that reaction produces, and obtains aqueous catalyst solution, removes after moisture, and catalyst can be recycled.
Embodiment 5
Technical process in the present embodiment and step are identical with embodiment 4, and different is that ionic liquid catalyst is by [hmim] Cl and FeCl
3be that 1:1.5 is formulated in molar ratio, reaction temperature is controlled at 180 DEG C, finally obtains more gaseous products, and gaseous products is to be mainly H
2, CO, CH
4, CO
2.
Embodiment 6
Getting particle diameter is 50 object biomass castoff-----stalk butt 20g and [hmim] Cl/ZnCl
2-NiCl
2the ionic liquid catalyst of composition mixes ([hmim] Cl, ZnCl
2and NiCl
2three's mol ratio is 1:0.5:1), be placed in quartz reactor; The weight proportion of butt and catalyst is 1:3, adds catalyst 60g; Closed reactor, passes into nitrogen, discharges remaining air in reactor; Quartz reactor is positioned in the microwave of 2450 megahertzes, opens microwave heating equipment, it is 210 DEG C that pyrolysis reaction temperature is made as, reaction 30min, and the reacting gas product of generation is through condensing unit condensation and collect respectively condensate liquid and cooled gaseous product; After having reacted, the material after pyrolysis adds a small amount of water, and high speed centrifugation liquid is removed the residue that reaction produces, and obtains aqueous catalyst solution, removes after moisture, and catalyst can be recycled.
Claims (1)
1. a method for ionic liquid catalyst catalysis biomass discarded object liquefaction gasification, is characterized in that carrying out as follows:
(1) particle diameter biomass castoff drying, pulverizing, screening being made after processing is that 10～60 object particle powders mix mutually with ionic liquid catalyst, biomass castoff powder is after the ratio of 1:0.03～15 is mixed by weight percentage with ionic liquid catalyst, mixture is positioned in reactor, before pyrolytic reaction, pass into the surplus air in nitrogen purge reactor, carry out under oxygen free condition to ensure reaction, heat temperature raising, temperature is controlled in 160～300 DEG C of temperature ranges, and the reaction time is 10～50 minutes;
(2) gaseous mixture producing in pyrolytic reaction is cooling by condensing unit, collect condensed product in container, obtain required thermal decomposition product, residue in reactor is added to a small amount of water, after high speed centrifugation, remove residue, the ionic liquid catalyst aqueous solution after dewatering, recyclable recycling;
In the time that thermal decomposition product is liquid phase lower-molecular substance, ionic liquid catalyst is a kind of acidic ionic liquid and KOH, Ca (OH)
2mixed liquor in molar ratio 1:0.05～2 ratio mixes the K that contains forming
+, Ca
2+ionic liquid catalyst;
Described acidic ionic liquid is [HSO
3-bpy] CF
3sO
3, [HSO
3-bvim] HSO
3, [HSO
3-b-N (CH
3)
3] HSO
3,
；
In the time that thermal decomposition product is gas phase lower-molecular substance, ionic liquid catalyst is a kind of slaine to be had compared with the ionic liquid of high-solvency and Fe
3+and/or Ni
2+the slaine catalyst that 1:0.05～3 ratio is mixed to form in molar ratio;
Described to slaine have compared with the ionic liquid of high-solvency be chlorination 1-butyl-3-methylimidazole salt ([bmim] Cl), 1-butyl-3-methylimidazolium bromide salt ([bmim] Br), [emim] Cl, [hmim] Cl,
、
、
；
When described slaine or alkali are two kinds, between them, 1:0.05～2 are mixed to form mixed liquor in molar ratio.
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|---|---|---|---|
| CN201110268571.XA CN102441433B (en) | 2011-09-13 | 2011-09-13 | Ion liquid catalyst and method for liquefying and gasifying catalytic biomass waste thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110268571.XA CN102441433B (en) | 2011-09-13 | 2011-09-13 | Ion liquid catalyst and method for liquefying and gasifying catalytic biomass waste thereof |
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| Publication Number | Publication Date |
|---|---|
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| CN102441433B true CN102441433B (en) | 2014-07-30 |
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ID=46004663
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| CN103962116B (en) * | 2014-04-25 | 2015-09-09 | 南开大学 | A kind of load has the preparation method of the solid catalyst of cellulose body aid |
| CN105238434B (en) * | 2015-10-22 | 2017-03-08 | 昆明理工大学 | The method orienting regulation and control liquid-phase catalysis biomass through pyrolysis using magnetic ionic liquids |
| US11602737B2 (en) * | 2015-11-05 | 2023-03-14 | Reliance Industries Limited | Metal hydroxide based ionic liquid composition |
| CN109759131B (en) * | 2019-01-31 | 2021-10-26 | 河北科技大学 | Composite ionic liquid and method for catalytically synthesizing n-butyl carboxylate by using same |
| TWI728485B (en) * | 2019-10-02 | 2021-05-21 | 嘉藥學校財團法人嘉南藥理大學 | Ionic liquid catalyst |
| FI129246B (en) * | 2019-11-08 | 2021-10-15 | Valmet Technologies Oy | A method and a system for producing an oil rich fraction from biomass |
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