CN101845333A - Method for preparing biological oil with high alcohol content by catalytically cracking biomass through microporous-mesoporous composite molecular sieve - Google Patents
Method for preparing biological oil with high alcohol content by catalytically cracking biomass through microporous-mesoporous composite molecular sieve Download PDFInfo
- Publication number
- CN101845333A CN101845333A CN201010193943A CN201010193943A CN101845333A CN 101845333 A CN101845333 A CN 101845333A CN 201010193943 A CN201010193943 A CN 201010193943A CN 201010193943 A CN201010193943 A CN 201010193943A CN 101845333 A CN101845333 A CN 101845333A
- Authority
- CN
- China
- Prior art keywords
- biomass
- composite molecular
- molecular sieve
- cracking
- alcohol content
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000002028 Biomass Substances 0.000 title claims abstract description 56
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 53
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000005336 cracking Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000012075 bio-oil Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 235000011089 carbon dioxide Nutrition 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000010815 organic waste Substances 0.000 claims description 4
- 229920002488 Hemicellulose Polymers 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 210000003608 fece Anatomy 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 244000144972 livestock Species 0.000 claims description 3
- 239000010813 municipal solid waste Substances 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 244000144977 poultry Species 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 150000002240 furans Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000007233 catalytic pyrolysis Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 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
- 239000000203 mixture Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 alcohol compound Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000009466 transformation Effects 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
-
- 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
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to the biomass cracking technology, and discloses a method for preparing biological oil with high alcohol content by catalytically cracking biomass through a microporous-mesoporous composite molecular sieve. In a biomass cracking process, the microporous-mesoporous composite molecular sieve is used as a catalyst, the biomass and the like are used as processed materials, and the mass ratio of the composite molecular sieve to the biomass is 1:1-1:50. Protective gas is introduced into a reactor. At the reaction temperature of between 350 and 700 DEG C, the biomass is heated in the cracking reactor to depolymerize organic macromolecules. The cracking products comprise the biological oil, solid carbon and cracking gas. The method has the following advantages that: 1, the microporous-mesoporous composite molecular sieve is a good biomass cracking reaction catalyst, and the acidity and pore structure of the composite molecular sieve can be changed by adjusting the silicon-to-aluminum ratio of the micropores and the mesopores respectively; and 2, the biomass is catalytically cracked by using the microporous-mesoporous composite molecular sieve so that the method for preparing the biological oil with high alcohol content has mild process conditions, simple operation and good controllability.
Description
Technical field
The present invention relates to prepare the bio oil method, mainly is a kind of micropore--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through.
Background technology
Along with the surge and the industrial fast development of population, current society increases energy demand quantity.Because fossil energy is a large amount of to be used and brings environmental pollution and resource problem such as peter out, and makes the development and use of renewable energy source become more and more important.Biomass energy is as unique renewable energy source that can be converted into liquid fuel, because of its in a large number, exist widely, and be that a kind of eco-friendly green energy resource more and more comes into one's own.It is to be only second to coal, oil and natural gas and the energy that occupy the 4th of world energy sources total quantity consumed.The utilization of biomass energy can significantly reduce the total release of carbonic acid gas, thus effectively control " Greenhouse effect ".Biomass contain very low ash content usually, sulfur-bearing hardly, so when utilizing biomass as fuel, do not worry the pollution that sulphur forms and the processing of ash content, this makes it become the most attractive renewable energy source resource.
According to statistics, about 700,000,000 tons of the various agricultural crop straw annual production of China are commonly used for fuel, feed in the past.In recent years, along with the minimizing of above-mentioned utilization, most of discarded or burning in the field, a large amount of straw burning flue gases of discharging have caused environmental pollution in partial area, have reduced atmospheric visibility, even have influenced the landing of air station flight.
With Wood Adhesives from Biomass such as agriculture and forestry organic waste material, stalks is that energy density height, " bio oil " easy to use are importances of new energy development.Wood Adhesives from Biomass is that bio oil mainly contains fast pyrolysis and two kinds of methods of direct liquefaction.Fast pyrolysis is meant high-molecular biologic matter under hot conditions, and the flash thermolysis is micromolecular organic steam, is converted into bio oil through condensation.Bio oil belongs to rudimentary liquid fuel, contain 300 surplus kind of organic compound, and range of molecular weight distributions broad; Have strong oxidizing property, strongly-acid, to plain metal have severe corrosive, chemically with thermodynamics on unstable and be difficult for mixing mutually with oil fuel.These inferior fuel performances have suppressed bio oil and have been directly used in the present oil-burning apparatus.Can improve the bio oil fuel performance by shortening and catalyse pyrolysis.Catalytic pyrolysis is that the macromole organic steam that under catalyst action biomass fast pyrogenation is obtained further is cracked into less molecule, oxygen element is wherein removed with the form of H2O, CO and CO2, different with the harsh reaction conditions of required high pressure of shortening and hydrogen supply dissolvent, catalytic pyrolysis can carry out under condition of normal pressure, and does not need reducing gas.
The catalyzer that catalytic pyrolysis is commonly used has molecular sieve catalyst, metal and metal oxide etc.What wherein, use was maximum is molecular sieve catalyst.Micro porous molecular sieve is a shape-selective catalyst important in the modern petroleum industry, has the microvoid structure of even prosperity, the characteristics of acid strong and good hydrothermal stability, is used widely in a lot of fields.But because its aperture is less, macromole enters the duct difficulty, and diffusional resistance is bigger simultaneously, and the macromole that forms in its vestibule can not be overflowed fast, thereby has limited its application in bulky molecular catalysis transforms greatly.And mesopore molecular sieve can remedy the deficiency of micro porous molecular sieve, for macromolecular reaction provides favourable sterie configuration.But the strength of acid of mesopore molecular sieve is not enough, and hydrothermal stability is relatively poor, has limited its range of application equally.
Composite molecular screen is the molecular sieve with two or more pore passage structure.This molecular sieve with multiplet structure and overlaying function can be avoided the defective of single pore structure, the multistage pore canal system can provide size different ducts simultaneously, make two or more material advantage complementations, synergy, the molecular diffusion that helps the different sizes of component complexity arrives the catalyzer internal-response.Composite molecular screen has been applied to reactions such as heavy oit pyrolysis, isomerization, but does not see the report that is applied to biomass pyrolytic about composite molecular screen.
Summary of the invention
The present invention will solve the shortcoming of above-mentioned prior art, a kind of micropore is provided--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through, by synthetic composite molecular screen with little-meso-hole structure, the cracking process that is used for biomass, make full use of the duct advantage of mesopore molecular sieve and the strongly-acid and the high hydrothermal stability of micro porous molecular sieve, the steam that biomass through pyrolysis is produced carries out second pyrolysis.A kind of economical and effective, mild condition, simple to operate, method that biomass cracking that controllability good, cost is low is produced biological oil with high alcohol content are provided.
The present invention solves the technical scheme that its technical problem adopts: this micropore--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through, comprise the steps: with composite molecular screen that as catalyzer composite molecular screen is a micropore and mesoporous compound; With biomass is raw material; feed protection gas, temperature of reaction is 350-700 ℃, and the mass ratio of composite molecular screen and biomass is 1: 1～1: 50; biomass are heated in cracking reactor and are made organic polymer depolymerization, split product is solid carbon, bio oil and product gas.
By technical scheme of the present invention, described composite molecular screen is a micropore and mesoporous compound.During cracking, preferred cracking temperature is 400-550 ℃; The mass ratio of preferred composite molecular screen and biomass is 1: 5～1: 20; Protection gas can be nitrogen, argon gas, helium or carbonic acid gas; The cracked system pressure can be normal pressure, decompression; Composite molecular screen can directly mix with biomass, also can be placed apart, composite molecular screen is hung on reactor top.Biomass material is Mierocrystalline cellulose, hemicellulose, xylogen and agriculture and forestry organic waste material (as stalk, rice husk, wood chip, leaf, shell, fruit stone), municipal solid wastes or feces of livestock and poultry.
The preparation method of composite molecular screen is as follows: at first prepare micro porous molecular sieve ZSM-5 (38), with 0.152mol silicon sol+0.002mol Al
2(SO
4)
318H
2O+2.5mol H
2O+0.025mol n-Butyl Amine 99+0.026mol NaOH stirs, and regulating the pH value is 11,170 ℃ of crystallization 4d, and 550 ℃ of roasting 8h get ZSM-5 (38) molecular sieve; Prepare micropore then--mesoporous composite molecular sieve ZSM-5 (38)/Al-MCM-41 (40), with 0.038mol tetraethoxysilance+0.001mol Al (NO
3)
39H
2O+6.667mol H
2After stirring 2h under O+0.0046mol cetyl trimethylammonium bromide+0.033mol NaOH+1gZSM-5 (38) room temperature, in 100 ℃ of crystallization 3d, 550 ℃ of roasting 6h get ZSM-5 (38)/Al-MCM-41 (40) molecular sieve.
The effect that the present invention is useful is: 1, micropore--mesoporous composite molecular sieve is the good biomass cracking catalysts, can by adjust micropore respectively, mesoporous silica alumina ratio changes its acidity and pore structure.2, utilize micropore--mesoporous composite molecular sieve catalytic pyrolysis biomass, make the processing condition gentleness produce biological oil with high alcohol content, simple to operate, controllability good.3, compare with the biomass through pyrolysis that does not add catalyzer, at micropore--under the katalysis of mesoporous composite molecular sieve, alcohol compound content in the bio oil obviously increases, and compounds contents such as aldehydes, ketone, ester class, ethers, furans and acids reduce, and has improved the quality of bio oil.
Description of drawings
Fig. 1 biomass catalyzing thermo-cracking experiment process synoptic diagram.
Embodiment
The invention will be further described below in conjunction with drawings and Examples:
This micropore of the present invention--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through comprises the steps: with composite molecular screen as catalyzer, and composite molecular screen is a micropore and mesoporous compound; With biomass is raw material; feed protection gas, temperature of reaction is 350-700 ℃, and the mass ratio of composite molecular screen and biomass is 1: 1～1: 50; biomass are heated in cracking reactor and are made organic polymer depolymerization, split product is solid carbon, bio oil and product gas.
By technical scheme of the present invention, described composite molecular screen is a micropore and mesoporous compound.During cracking, preferred cracking temperature is 400-550 ℃; The mass ratio of preferred composite molecular screen and biomass is 1: 5～1: 20; Protection gas can be nitrogen, argon gas, helium or carbonic acid gas; The cracked system pressure can be normal pressure, decompression; Composite molecular screen can directly mix with biomass, also can be placed apart, composite molecular screen is hung on reactor top.Biomass material is Mierocrystalline cellulose, hemicellulose, xylogen and agriculture and forestry organic waste material, municipal solid wastes or feces of livestock and poultry.
By technical scheme of the present invention, described micropore--the mesoporous composite molecular sieve preparation method is following (with the example that is prepared as of ZSM-5 (38)/Al-MCM-41 (40), wherein: numerical value is represented silica alumina ratio respectively in ZSM-5 (38)/Al-MCM-41 (40) bracket, be that ZSM-5 (38) expression silica alumina ratio is 38 ZSM-5 type micro porous molecular sieve, Al-MCM-41 (40) expression silica alumina ratio is 40 Al-MCM-41 type mesopore molecular sieve.All the other type microporous-mesoporous composite molecular sieves described in the example are except that the silica alumina ratio difference, and the preparation method is identical therewith.)：
At first prepare micro porous molecular sieve ZSM-5 (38).With 0.152mol silicon sol+0.002mol Al
2(SO
4)
318H2O+2.5molH
2O+0.025mol n-Butyl Amine 99+0.026mol NaOH stirs, and regulating the pH value is 11,170 ℃ of crystallization 4d, and 550 ℃ of roasting 8h get ZSM-5 (38) molecular sieve.
Prepare micropore then--mesoporous composite molecular sieve ZSM-5 (38)/Al-MCM-41 (40).With 0.038mol TEOS (tetraethoxysilance)+0.001mol Al (NO
3)
39H
2O+6.667mol H
2After stirring 2h under O+0.0046mol CTAB (cetyl trimethylammonium bromide)+0.033mol NaOH+1gZSM-5 (38) room temperature, in 100 ℃ of crystallization 3d, 550 ℃ of roasting 6h get ZSM-5 (38)/Al-MCM-41 (40) molecular sieve.
After tested, the specific surface area of the ZSM-5 of preparation (38)/Al-MCM-41 (40) composite molecular screen is 749m3/g, and mean pore size is 2.5nm.
A kind of aforesaid micropore--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through, Fig. 1 is a primary structure synoptic diagram of the present invention.1-nitrogen; The 2-spinner-type flowmeter; The 3-heating jacket; The 4-reactor; The 5-condenser; The 6-receiving bottle; The 7-vacuum pump; The a-catalyst layer; B-is material bed.
Example 1:
The 10g Mierocrystalline cellulose is joined in the reactor, feed the air in the N2 displacement apparatus, reactor is heated to 450 ℃ again, heating rate is 30 ℃/min, vacuum tightness is to react under the 0.02MPa condition, and thermal cracking gas obtains bio oil in temperature for condensation in-10 ℃ the condenser.Gained bio oil 4.67g, solid carbon 1.38g, splitting gas 3.86g.Pure content is 20.4% in the bio oil, and hydro carbons is 3.8%, and ketone is 8.0%, and aldehydes is 12.1%, and the ester class is 18.4%, and ethers is 14.1%, and furans is 12.3%, and aromatics is 5.9%, and acids is 5.0%.
Example 2,3,4:
Extracting cellulose 10g, catalyzer 1g, other reaction conditionss are with example 1.Catalyst system therefor is respectively ZSM-5 (38)/Al-MCM-41 (20), ZSM-5 (38)/Al-MCM-41 (40), ZSM-5 (38)/Al-MCM-41 (60) type microporous-mesoporous composite molecular sieve, places raw material top respectively.The gained bio oil is respectively 4.46,3.95,3.75g, and solid carbon is respectively 1.35,1.04,1.32g, splitting gas is respectively 4.19,5.01,4.93g.Compare with example 1, pure content all has tangible increase in the gained bio oil, is increased to 36.8%, 33.6%, 36.5% respectively by 20.4%, and aldehyde, ester, ether, furans and acid content all have minimizing to a certain degree in addition.
Example 5,6:
Extracting cellulose 10g, catalyzer 1g, other reaction conditionss are with example 1.Catalyst system therefor is respectively ZSM-5 (50)/Al-MCM-41 (20), ZSM-5 (50)/Al-MCM-41 (80) type microporous-mesoporous composite molecular sieve, places raw material top respectively.The gained bio oil is respectively 4.55,4.57g, and solid carbon is 1.45g, and splitting gas is respectively 4.00,3.98g.Compare with example 1, pure content all has tangible increase in the gained bio oil, is increased to 28.8%, 28.5% respectively by 20.4%, and aldehyde, ether, furans content all have minimizing to a certain degree.
Example 7,8:
Rice straw 10g is joined in the reactor, feed the air in the N2 displacement apparatus, reactor is heated to 500 ℃ again, heating rate is 30 ℃/min, normal pressure, do not adding catalyzer and adding under 1g ZSM-5 (38)/Al-MCM-41 (40) type microporous-mesoporous composite molecular sieve catalyzer condition and react respectively, catalyzer and raw material uniform mixing are placed in the reactor.Thermal cracking gas obtains bio oil in temperature for condensation in-10 ℃ the condenser.Pure content is respectively 14.6%, 30.5% in the bio oil, and aldehyde, ester, ether, furans and acid content all have minimizing to a certain degree.
In addition to the implementation, all employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (8)
1. a micropore--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through is characterized in that: comprise the steps: with composite molecular screen that as catalyzer composite molecular screen is a micropore and mesoporous compound; With biomass is raw material; feed protection gas, temperature of reaction is 350-700 ℃, and the mass ratio of composite molecular screen and biomass is 1: 1～1: 50; biomass are heated in cracking reactor and are made organic polymer depolymerization, split product is solid carbon, bio oil and product gas.
2. micropore according to claim 1--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through is characterized in that: during cracking, the temperature in the reactor is 400-550 ℃.
3. micropore according to claim 1--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through is characterized in that: protection gas is nitrogen, argon gas, helium or carbonic acid gas.
4. micropore according to claim 1--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through is characterized in that: during cracking, the mass ratio of composite molecular screen and biomass is 1: 5～1: 20.
5. micropore according to claim 1--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through is characterized in that: composite molecular screen directly mixes with biomass; Or placed apart, composite molecular screen is hung on reactor top.
6. micropore according to claim 1--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through is characterized in that: biomass are Mierocrystalline cellulose, hemicellulose, xylogen and agriculture and forestry organic waste material, municipal solid wastes or feces of livestock and poultry.
7. micropore according to claim 1--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through is characterized in that: the cracked system pressure is normal pressure or decompression.
8. micropore according to claim 1--the method for mesoporous composite molecular sieve preparing biological oil with high alcohol content by catalytically cracking biomass through, it is characterized in that: the preparation method of composite molecular screen is as follows: at first prepare micro porous molecular sieve ZSM-5 (38), with 0.152mol silicon sol+0.002mol Al
2(SO
4)
318H
2O+2.5mol H
2O+0.025mol n-Butyl Amine 99+0.026mol NaOH stirs, and regulating the pH value is 11,170 ℃ of crystallization 4d, and 550 ℃ of roasting 8h get ZSM-5 (38) molecular sieve; Prepare micropore then--mesoporous composite molecular sieve ZSM-5 (38)/Al-MCM-41 (40), with 0.038mol tetraethoxysilance+0.001mol Al (NO
3)
39H
2O+6.667mol H
2After stirring 2h under O+0.0046mol cetyl trimethylammonium bromide+0.033mol NaOH+1gZSM-5 (38) room temperature, in 100 ℃ of crystallization 3d, 550 ℃ of roasting 6h get ZSM-5 (38)/Al-MCM-41 (40) molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010193943A CN101845333A (en) | 2010-06-03 | 2010-06-03 | Method for preparing biological oil with high alcohol content by catalytically cracking biomass through microporous-mesoporous composite molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010193943A CN101845333A (en) | 2010-06-03 | 2010-06-03 | Method for preparing biological oil with high alcohol content by catalytically cracking biomass through microporous-mesoporous composite molecular sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101845333A true CN101845333A (en) | 2010-09-29 |
Family
ID=42770151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010193943A Pending CN101845333A (en) | 2010-06-03 | 2010-06-03 | Method for preparing biological oil with high alcohol content by catalytically cracking biomass through microporous-mesoporous composite molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101845333A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634357A (en) * | 2012-04-13 | 2012-08-15 | 华北电力大学 | Method for preparing liquid fuel through mesoporous silica hollow sphere based catalyst |
| CN102660309A (en) * | 2012-04-13 | 2012-09-12 | 华北电力大学 | Method for preparing biomass base liquid fuel by using ordered mesoporous ZrO2-base catalyst |
| CN102660308A (en) * | 2012-04-13 | 2012-09-12 | 华北电力大学 | Method for preparing biomass base liquid fuel by using ordered mesoporous TiO2-base catalyst |
| CN104355968A (en) * | 2014-10-20 | 2015-02-18 | 北京林业大学 | Method for preparing phenolic substances through catalytic pyrolysis conversion of cellulose |
| CN104549476A (en) * | 2015-01-12 | 2015-04-29 | 天津大学 | Nickel metal loaded micro-mesoporous molecular sieve catalyst precursor and preparation method and application of nickel metal loaded micro-mesoporous molecular sieve catalyst precursor |
| CN105126901A (en) * | 2015-09-14 | 2015-12-09 | 青岛大学 | Molecular sieve catalyst applied to seaweed liquefaction reaction and preparation method thereof |
| CN112300818A (en) * | 2020-11-06 | 2021-02-02 | 赵海玲 | Method for preparing bio-oil by coupling biomass pyrolysis and methane aromatization |
| CN115261055A (en) * | 2022-07-28 | 2022-11-01 | 青岛科技大学 | Method for preparing biofuel by catalytic cracking of waste oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090126260A1 (en) * | 2007-09-18 | 2009-05-21 | Sapphire Energy, Inc | Methods of refining hydrocarbon feedstocks |
| CN101514295A (en) * | 2009-03-26 | 2009-08-26 | 四川大学 | Method for preparing bio-oil by catalytic pyrolysis of microalgae with high fat content by molecular sieve |
-
2010
- 2010-06-03 CN CN201010193943A patent/CN101845333A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090126260A1 (en) * | 2007-09-18 | 2009-05-21 | Sapphire Energy, Inc | Methods of refining hydrocarbon feedstocks |
| CN101514295A (en) * | 2009-03-26 | 2009-08-26 | 四川大学 | Method for preparing bio-oil by catalytic pyrolysis of microalgae with high fat content by molecular sieve |
Non-Patent Citations (2)
| Title |
|---|
| FAROUQ A. ET AL: "Performance of composite catalysts in palm oil cracking for the production of liquid fuels and chemicals", 《FUEL PROCESSING TECHNOLOGY》 * |
| 鲍卫仁 等: "MCM-41 /SBA-15中孔分子筛对生物质热解油的催化裂解研究", 《燃料化学学报》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634357A (en) * | 2012-04-13 | 2012-08-15 | 华北电力大学 | Method for preparing liquid fuel through mesoporous silica hollow sphere based catalyst |
| CN102660309A (en) * | 2012-04-13 | 2012-09-12 | 华北电力大学 | Method for preparing biomass base liquid fuel by using ordered mesoporous ZrO2-base catalyst |
| CN102660308A (en) * | 2012-04-13 | 2012-09-12 | 华北电力大学 | Method for preparing biomass base liquid fuel by using ordered mesoporous TiO2-base catalyst |
| CN102660308B (en) * | 2012-04-13 | 2014-07-16 | 华北电力大学 | Method for preparing biomass base liquid fuel by using ordered mesoporous TiO2-base catalyst |
| CN102660309B (en) * | 2012-04-13 | 2014-08-06 | 华北电力大学 | Method for preparing biomass base liquid fuel by using ordered mesoporous ZrO2-base catalyst |
| CN104355968A (en) * | 2014-10-20 | 2015-02-18 | 北京林业大学 | Method for preparing phenolic substances through catalytic pyrolysis conversion of cellulose |
| CN104355968B (en) * | 2014-10-20 | 2015-12-30 | 北京林业大学 | A kind of cellulose catalytic thermo-cracking transforms the method preparing aldehydes matter |
| CN104549476A (en) * | 2015-01-12 | 2015-04-29 | 天津大学 | Nickel metal loaded micro-mesoporous molecular sieve catalyst precursor and preparation method and application of nickel metal loaded micro-mesoporous molecular sieve catalyst precursor |
| CN104549476B (en) * | 2015-01-12 | 2017-12-12 | 天津大学 | A kind of micro- mesoporous molecular sieve catalyst presoma of nickel Metal Supported and Preparation method and use |
| CN105126901A (en) * | 2015-09-14 | 2015-12-09 | 青岛大学 | Molecular sieve catalyst applied to seaweed liquefaction reaction and preparation method thereof |
| CN112300818A (en) * | 2020-11-06 | 2021-02-02 | 赵海玲 | Method for preparing bio-oil by coupling biomass pyrolysis and methane aromatization |
| CN115261055A (en) * | 2022-07-28 | 2022-11-01 | 青岛科技大学 | Method for preparing biofuel by catalytic cracking of waste oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101845333A (en) | Method for preparing biological oil with high alcohol content by catalytically cracking biomass through microporous-mesoporous composite molecular sieve | |
| CN103992144B (en) | A kind of method being prepared nitrogenous carbon material by biomass pyrolytic carbonization | |
| CN102936511B (en) | Method for producing high-grade bio-oil through on-line catalytic cracking of biomass flash pyrolysis product | |
| CN108865196A (en) | A kind of charcoal preparation method | |
| CN104479720B (en) | Living beings binary catalyst pyrolysis high yield is produced the method and apparatus of hydrocarbon compound | |
| CN101514295B (en) | Method for preparing bio-oil by catalytic pyrolysis of microalgae with high fat content by molecular sieve | |
| CN104560225B (en) | A kind of biomass produce the method for high-quality oil fuel | |
| CN107337587A (en) | A kind of method that rich phenol liquid oil is prepared using biomass | |
| CN104725229A (en) | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate | |
| CN105899293B (en) | The method for transformation of the pyrolysis oil of biomass derived, the method and catalyst for preparing catalyst | |
| CN108671960A (en) | A kind of high hydrothermal stability MOFs catalyst, the method for preparing and preparing chemicals for cellulose conversion | |
| EP2995672B1 (en) | Method for modifying biomass pyrolysis oil | |
| CN105597806A (en) | Hydrodeoxygenation cobalt catalyst and preparation method thereof | |
| KR101301696B1 (en) | Novel metal catalyst suppored on activated carbon aerogel bearing acid site, preparation method thereof and decomposition of lignin compound using said catalyst | |
| CN109054875A (en) | A kind of biomass efficient method for transformation | |
| KR20120094555A (en) | Novel metal catalyst supported on activated carbon aerogel, production method thereof and decomposition method of lignin compound using said catalyst | |
| CN103666514B (en) | Method for on-line catalytic cracking of biomass through gushing bed-revolving bed two-step method | |
| CN106241770A (en) | A kind of preparation method of bamboo base porous carbon | |
| CN106890669A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| KR101298688B1 (en) | Novel metal catalyst supported on activated carbon aerogel bearing cation-exchanged heteropolyacid and decomposition method of lignin compounds using said catalyst | |
| CN105251524B (en) | Biomass liquefied oil catalytic cracking dehydrogenation catalyst | |
| Dhawane et al. | Synthesis of Catalyst Support from Waste Biomass for Impregnation of Catalysts in Biofuel Production | |
| XIAO et al. | One-pot catalytic agroforestry waste cellulose to polyols over self-reducing bifunctional catalysts | |
| CN107159307A (en) | A kind of sial phosphorus molecular sieve of carried metal and application | |
| CN102660309B (en) | Method for preparing biomass base liquid fuel by using ordered mesoporous ZrO2-base catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100929 |