CN101863736B - Method for preparing biomass-based methanol - Google Patents
Method for preparing biomass-based methanol Download PDFInfo
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- CN101863736B CN101863736B CN201010190095XA CN201010190095A CN101863736B CN 101863736 B CN101863736 B CN 101863736B CN 201010190095X A CN201010190095X A CN 201010190095XA CN 201010190095 A CN201010190095 A CN 201010190095A CN 101863736 B CN101863736 B CN 101863736B
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- 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
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- 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
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- 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
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Abstract
The invention provides a method for preparing biomass-based methanol, which comprises the following steps: a) cracking biomass to form biological oil vapor and biomass carbon powder; b) performing gas-solid separation of the biological oil vapor and performing a water vapor reforming reaction to obtain a biological oil reformed synthesis gas; c) grinding and mixing the biomass carbon powder, a catalyst and a bonding agent, drying the mixture, performing a reduction reaction by using hydrogen, heating the product of the reduction, performing a coal gasification reaction and a reverse coal gasification reaction of the product of the reduction and the biological oil reformed synthesis gas, condensing and drying the obtained mixed gas to obtain biomass reformed-modified synthesis gas; and d) performing a synthesis reaction of the biomass reformed-modified synthesis gas, condensing the obtained reaction tail gas, and obtaining the biomass-based methanol from a liquid product. The method can effectively convert a biomass-based synthesis gas into the biomass-based methanol, uses the rich, environmentally-friendly and renewable biomass as a raw material, achieves high methanol yield and selectively, makes reaction conditions mild and can be used for industrial production.
Description
Technical field
The present invention relates to chemical field, be specifically related to a kind of method of preparing biomass-based methanol.
Background technology
The energy is the mainstay of human survival and Sustainable Socioeconomic Development.Along with the pressure of energy demand and environment protection increases rapidly; utilizing reproducible biomass energy to be subject to people pays close attention to greatly; point out in " China 21st century population, environment and development white paper ": " we must be put into the renewable cleaning new energy of development and use and new resources the precedence of national energy development strategy, strengthen the exploitation of biomass energy.", United Nations Conference on Environment and Development expects the year two thousand fifty biomass utilization and will account for about half of global Energy Consumption.Biomass are with its aboundresources, environmental friendliness, the advantage such as renewable and become a kind of up-and-coming production clean fuel liquid starting material, from utilization of resources and green circulation economy angle, the chemical of producing higher-grade liquid fuel and high added value by bio oil has broad application prospects.
Methyl alcohol is basic organic chemical raw material and high-grade fuel, methyl alcohol is mainly used in the fields such as fine chemistry industry, plastics, as be used for making the multiple organic productss such as formaldehyde, acetic acid, methyl chloride, first ammonia, methyl-sulfate, methyl alcohol also is one of important source material of agricultural chemicals, medicine, in addition, methyl alcohol can add gasoline to and form the methanol gasoline vehicle fuel.The production of methyl alcohol starts from nineteen twenty-three, and BASF Aktiengesellschaft at first adopts Zn-Cr oxide catalyst synthetic methanol product that obtains under 30MPa-35MPa, 300 ℃ of-400 ℃ of conditions.At present, the raw material of industrial methanol mainly is coal, Sweet natural gas and petroleum naphtha, present methanol synthesizing process is the gas phase low-pressure synthesis, main technique is to utilize CuZnAl catalyzer and shell and tube-type reactor synthesizing methanol under 200 ℃-300 ℃, the condition of 5MPa-6MPa (to be called for short the strange low-pressure process in Shandong, patent: CN97104816.9).
Biomass-based methanol is synthetic to be to utilize catalyzing and reforming biologic oil or gasifying biomass to obtain Biomass Syngas, obtain biomass-based methanol by catalyzing and synthesizing again by Biomass Syngas, the advantage of the method maximum be have that raw material is renewable, in the product sulphur content low, without CO
2Discharging and the advantage that is not subjected to the biomass class limitations, the synthetic development that still is in of present biomass-based methanol, the key technical problem that needs to solve is raising methanol yield and selectivity of product.Although using reproducible biomass-making biomass-based methanol is a kind of green economy pattern capable of circulation, the country that lacks petroleum resources is had more very strong economy and suitability, but, since actual Biomass Syngas complicated components and with the factor analysis such as biomass material type, preparation synthesis gas reaction technique, carrier gas, reaction conditions, generally comprise H
2, CO, CO
2, multiple hydrocarbon thing is (such as CH
4, C
2H
4) and the component, the particularly Biomass Syngas by biological oil reforming production such as moisture in comprise very a high proportion of CO
2(CO
2Volumetric concentration can reach 20vol%-35vol%, CO
2Volumetric concentration is 6.33 with CO volumetric concentration ratio, patent: CN101177239A; CN101306370; CN200910116098.6), need to solve carbon dioxide enriched synthetic gas biomass-based methanol problem processed; Compare as the raw material methanol synthetizing technology with present coal, the Sweet natural gas of using, utilize Biomass Syngas to produce methanol yield and selectivity [document: Xiuli Yin and Dennis Y.C.Leung, Energy ﹠amp on the low side that methanol technics obtains; Fuels 2005,19,305-310], far do not reach the level of suitability for industrialized production.
Summary of the invention
The problem that the present invention solves is to provide a kind of method of preparing biomass-based methanol, and methanol yield and selectivity are higher.
In order to solve the problems of the technologies described above, technical scheme of the present invention is:
A kind of method of preparing biomass-based methanol may further comprise the steps:
A) biomass cracking is generated bio oil steam and biomass charcoal powder;
B) described bio oil steam carries out steam reforming reaction after gas solid separation, gets coarse biometric oil reformation synthetic gas;
C) with biomass charcoal powder, catalyzer and associating agent ground and mixed, the mixed powder that obtains is dry, under the hydrogen condition, reduce post-heating, pass into described coarse biometric oil reformation synthetic gas and carry out coal gas reaction and reverse water-gas reaction, the Mixed Gas Condensation that reaction is obtained, the dry synthetic gas of must biomass reforming-adjust;
D) described biomass are reformed-adjusted synthetic gas carries out building-up reactions, and the reaction end gas that obtains carries out condensation, obtains biomass-based methanol in the liquid product of collecting.
As preferably, described a) in biomass be in stalk, wood chip or the rice husk one or more.
As preferably, described c) mass ratio of biomass charcoal powder and catalyzer is 1: 0.5～1 in, and the mass percent that described associating agent accounts for described mixed powder is 3%～10%.
As preferably, described catalyzer is that mass parts is 1: 0.8～1.2 NiO-Al
2O
3Form with HZSM-5.
As preferably, described NiO-Al
2O
3Middle NiO accounts for NiO-Al
2O
3Mass percent be 17%～19%.
As preferably, the mol ratio of silicon, aluminium is 25 among the described HZSM-5.
As preferably, described associating agent is one or both in kaolin or the sesbania powder.
As preferably, described c) the mixed powder drying that obtains in is specially at 100 ℃～120 ℃ lower dry 9h～11h.
As preferably, also sieve after the described mixed powder drying, the mixed powder that sieves out particle diameter and be 0.25mm～0.38mm reduces.
As preferably, described c) reaction is specially dried mixed powder is filled in the reactor, at High Purity Hydrogen, 490 ℃～510 ℃ lower reduction 55min～65min, after being heated to 400 ℃～800 ℃, coarse biometric oil reformation synthetic gas is issued soft coal solid/liquid/gas reactions and reverse water-gas reaction with biomass charcoal powder at catalyst action after 180 ℃～200 ℃ preheating.
As preferably, described c) reaction is specially dried mixed powder is filled in the reactor of built-in electric stove wire, and contact with the electric stove wire surface uniform, at High Purity Hydrogen, 490 ℃～510 ℃ lower reduction 55min～65min, after being heated to 400 ℃～800 ℃, coarse biometric oil reformation synthetic gas is issued soft coal solid/liquid/gas reactions and reverse water-gas reaction with biomass charcoal powder at catalyzer and galvanic action after 180 ℃～200 ℃ preheating.
As preferably, described built-in electric stove wire is selected Ni-Cr electric stove wire or Fe-Cr-Ar electric stove wire.
As preferably, the electric current of described electric stove wire is 2.0A～4.0A.
As preferably, the reaction pressure of described coal gas reaction and reverse water-gas reaction is 1atm～1.2atm, and the reaction flow velocity is 40ml/min～100ml/min.
Also add synthetic catalyst when carrying out building-up reactions as preferably, described d), described synthetic catalyst is CuZnAl catalyst, and mass percent consists of: 55%～65%CuO, 25%～35%ZnO and 5%～15%Al
2O
3
As preferably, before carrying out building-up reactions, described synthetic catalyst is 9%～11% in volume percent, flow velocity is to heat up under the hydrogen reducing atmosphere of 95ml/min～105ml/min, temperature rise rate is 2 ℃/min～3 ℃/min, be warming up to 235 ℃～245 ℃, keep 19h～21h, then be down to room temperature.
As preferably, the temperature of described building-up reactions is 220 ℃～300 ℃, and pressure is 4.5MPa～5.5MPa, and air speed is 9000h
-1～11000h
-1
The method of preparing biomass-based methanol provided by the invention, can effectively Biomass Syngas be changed into biomass-based methanol, use various biomass to be raw material, have aboundresources, environmental friendliness and reproducible advantage, what obtain is biomass-based without sulphur, and methanol yield and selectivity are high, and reaction conditions is gentle, can be used for suitability for industrialized production, realized the sustainability recycle of resource-energy-environmental integration.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just as further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The method of preparing biomass-based methanol provided by the invention may further comprise the steps:
A) under the water vapour atmosphere condition, biomass are cracked into bio oil steam in the biomass cracking fluidized-bed, generate simultaneously the by product biomass charcoal powder, biomass are one or more in stalk, wood chip or the rice husk.
B) the bio oil steam that obtains enters after gas solid separation in the organic steam reformation fluidized-bed and carries out steam reforming reaction, obtains coarse biometric oil reformation synthetic gas, wherein is rich in carbonic acid gas.
C) biomass charcoal powder that will obtain, catalyzer and associating agent are mixed to get mixed powder after grinding, wherein the mass ratio of biomass charcoal powder and catalyzer be preferably 1: 0.5～1, the mass percent that the associating agent accounts for described mixed powder is 3%～10%.Catalyzer can be 1: 0.8～1.2 NiO-Al by mass parts
2O
3Form NiO-Al with HZSM-5
2O
3Middle NiO accounts for NiO-Al
2O
3The mass percent mol ratio that is preferably silicon among 17%～19%, the HZSM-5, aluminium be preferably 25; The associating agent can be selected one or both in kaolin or the sesbania powder.
Then mixed powder is carried out drying, preferably at 100 ℃～120 ℃ lower dry 9h～11h.Preferably also mixed powder is sieved after the drying, sieve out the mixed powder that particle diameter is 0.25mm～0.38mm, join again in the reactor and react with coarse biometric oil reformation synthetic gas.The reaction of biomass charcoal powder and coarse biometric oil reformation synthetic gas can only be carried out under the effect of catalyzer, also can carry out under the effect of catalyzer and electric current.
The reaction of only carrying out under the effect of catalyzer is specially dried mixed powder is filled in the reactor, at High Purity Hydrogen, 490 ℃～510 ℃ lower reduction 55min～65min, after being heated to 400 ℃～800 ℃, coarse biometric oil reformation synthetic gas is passed in the reactor after 180 ℃～200 ℃ preheating zone preheating, make carbonic acid gas and biomass charcoal powder in the coarse biometric oil reformation synthetic gas issue soft coal solid/liquid/gas reactions and reverse water-gas reaction at catalyst action, the Mixed Gas Condensation that reaction is obtained, the dry synthetic gas of must biomass reforming-adjust.
Also the preferred while reacts under the effect of electric current, be specially dried mixed powder is filled in the reactor of built-in electric stove wire, and contact with the electric stove wire surface uniform, built-in electric stove wire is selected Ni-Cr electric stove wire or Fe-Cr-Ar electric stove wire, electric current is preferably 2.0A～4.0A, then in High Purity Hydrogen, 490 ℃～510 ℃ lower reduction 55min～65min, after being heated to 400 ℃～800 ℃, coarse biometric oil reformation synthetic gas is passed in the reactor after 180 ℃～200 ℃ preheating zone preheating, make carbonic acid gas and biomass charcoal powder in the coarse biometric oil reformation synthetic gas issue soft coal solid/liquid/gas reactions and reverse water-gas reaction at catalyst action, the Mixed Gas Condensation that reaction is obtained, dry the biomass synthetic gas of reforming-adjust.
Wherein the reaction formula of coal gas reaction is: CO
2+ C → 2CO; The reaction formula of reverse water-gas reaction is: CO
2+ H
2→ CO+H
2O.The present invention effectively is converted into carbon monoxide with the carbonic acid gas in the coarse biometric oil reformation synthetic gas, can improve significantly the productive rate of preparing biomass-based methanol.
D) biomass that obtain are reformed-adjusted synthetic gas is input to and carries out building-up reactions in the high-pressure reactor that synthetic catalyst is housed, synthetic catalyst can be selected CuZnAl catalyst, and its mass percent composition is preferably: 55%～65%CuO, 25%～35%ZnO and 5%～15%Al
2O
3Before building-up reactions, preferably synthetic catalyst is carried out pre-treatment, be 9%～11% with synthetic catalyst in volume percent, flow velocity is to heat up under the hydrogen reducing atmosphere of 95ml/min～105ml/min, temperature rise rate is 2 ℃/min～3 ℃/min, be warming up to 235 ℃～245 ℃, keep 19h～21h, then be down to room temperature.The temperature of building-up reactions is preferably 220 ℃～300 ℃, and pressure is 4.5MPa～5.5MPa, and air speed is 9000h
-1～11000h
-1After building-up reactions finishes, with the reaction end gas condensation that obtains, in the liquid product of collecting, can obtain biomass-based methanol.
Embodiment 1:
Utilize biomass charcoal powder under the effect of catalyzer, to adjust coarse biometric oil reformation synthetic gas.
Take the wood chip powder as raw material, coarse biometric oil reformation synthetic gas uses series fluidized bed apparatus system (patent: CN200910116098.6) preparation: under the water vapour atmosphere condition, the wood chip powder is cracked into bio oil steam in the biomass cracking fluidized-bed, then bio oil steam enters after gas solid separation in the organic steam reformation fluidized-bed and carries out steam reforming reaction, organism in the bio oil steam is restructured as coarse biometric oil reformation synthetic gas, main component and the content of coarse biometric oil reformation synthetic gas of making waste of the wood chip powder is as shown in table 1, it is characterized in that Fu Qing and carbon dioxide enriched synthetic gas (H
2/ CO=16.73, CO
2/ CO=6.33).In addition, biomass charcoal powder is that biomass cracking generates by product in the bio oil steam course (patent: CN200910116098.6), coarse biometric oil reformation synthetic gas and biomass charcoal powder are as preparing bio-oil reform-the adjust reactant of synthetic gas.The catalyzer that uses in coarse biometric oil reformation synthetic gas adjustment process is that mass ratio is 1: 1 18%NiO-Al
2O
3And HZSM-5 (Si:Al=25) mixed catalyst.
Main component and the content of table 1 coarse biometric oil reformation synthetic gas
| Main component | H 2 | CO | CO 2 | N 2 | CH 4 | Other | [CO 2]/[CO] |
| Content, vol% | 68.59 | 4.10 | 25.97 | 0.95 | 0.28 | 0.11 | 6.33 |
In the preparation process, biomass charcoal powder catalysis is adjusted coarse biometric oil reformation synthetic gas and carried out in continuous flow fixed catalytic bed reactor-gas-chromatography combined system: this system comprises a tubular quartz reactor (internal diameter: Φ 30mm, length: 50cm) and the reactant (coarse biometric oil reformation synthetic gas) that is connected to both ends pass into pipeline and reaction end gas output channel, and be respectively equipped with control valve and reactant flow amount controller, the tubular quartz reactor is heated by outer electric furnace, and the access tube pipeline outer wall is provided with the external heating device for preheating; At first pass through condenser and moisture eliminator from the reaction end gas of reactor outlet discharging, taken a sample by the gas-chromatography six-way valve again, and unite with the TCD of GC-6890 gas chromatograph and FID and to do on-line analysis, two chromatographic column TDX-01 (3m) and PorapakQ-S (3m) are used for respectively detecting CO, CO
2, H
2, CH
4, N
2
Biomass charcoal powder is adjusted coarse biometric oil reformation synthetic gas under the effect of catalyzer detailed process is: the 18%NiO-Al that at first with biomass charcoal powder, mass ratio is 1: 1
2O
3And HZSM-5 (Si:Al=25) mixed catalyst, kaolin carry out by a certain percentage ground and mixed and obtain mixed powder, with above-mentioned mixed powder under the condition of 100 ℃ of temperature dry 10 hours, sieving obtained biomass charcoal powder and the catalyst mixture finished product that particle diameter is 0.25mm-0.38mm; Biomass charcoal powder and the catalyst mixture that obtains is filled in the tubular quartz reactor, 500 ℃ were reduced 1 hour under High Purity Hydrogen, by reactor indirect heating stove biomass charcoal powder and catalyst mixture were heated to 400 ℃-800 ℃ of temperature of reaction again; Raw material coarse biometric oil reformation synthetic gas is passed in the barrel reactor inlet pipe preheating zone, enter in the barrel reactor after 180 ℃ of-200 ℃ of lower preheatings, make carbonic acid gas and biomass charcoal powder in the coarse biometric oil reformation synthetic gas issue soft coal solid/liquid/gas reactions and reverse water-gas reaction at catalyst action; Reacted mixed gas is obtained biological oil reforming-adjustment synthetic gas after through the tail gas collection system that comprises condenser, moisture eliminator.Wherein, catalyzer and biomass charcoal powder mass ratio are 1.0, and kaolin accounts for the 5wt% of total mixed powder quality, and reaction pressure is normal pressure 1atm, and the reaction flow velocity is 60ml/min.
Table 2 has provided the effect of utilizing biomass charcoal powder to adjust coarse biometric oil reformation synthetic gas under the effect of catalyzer.Can find out from this table: when 800 ℃ of temperature of reaction, CO in the reactant synthetic gas
2Transformation efficiency (is pressed the CO of actual consumption
2CO in mole number and the reactant
2The ratio calculation of mole number) be that 74.4%, CO productive rate is (by every mole of CO
2Generating the CO mole number calculates) be 0.91mol CO/mol CO
2, can make rich CO
2Coarse biometric oil reformation synthetic gas ([CO
2Vol%] with [CO vol%] than being 6.33) effectively be converted into the biological oil reforming of rich CO-adjustment synthetic gas ([CO
2Vol%] with [CO vol%] than being 0.24).
Table 2 biomass charcoal powder is adjusted the effect of coarse biometric oil reformation synthetic gas under the effect of catalyzer
Embodiment 2:
Utilize biomass charcoal powder under the effect of catalyzer and electric current, to adjust coarse biometric oil reformation synthetic gas.
Present embodiment is take the wood chip powder as raw material, and coarse biometric oil reformation synthetic gas, biomass charcoal powder are identical with embodiment 1 with catalyzer.Reaction unit is that (patent: CN200710134707.1): it comprises (an internal diameter: Φ 30mm of the tubular reforming reactor with thermal insulation layer to the electrocatalysis reforming reactor, length: 50cm) and the reactant (biological oil reforming synthetic gas) that is connected to both ends pass into pipeline and reformation tail gas output channel, and being respectively equipped with control valve and reactant flow amount controller, the access tube pipeline outer wall is provided with the external heating device for preheating; Be connected with the tail gas collection system that comprises water vapor condensation device and moisture eliminator in turn at output channel; Be provided with the electric stove wire that ceramic insulating layer is communicated with external source in the inner chamber of tubular reforming reactor, the power of electric stove wire is selected by desired reaction temperature and reforming reactor volume, and built-in electric stove wire is the Ni-Cr electric stove wire; At first pass through condenser and moisture eliminator from the reaction end gas of reactor outlet discharging, taken a sample by the gas-chromatography six-way valve again, unite with the TCD of GC-6890 gas chromatograph and FID and to do on-line analysis, two chromatographic column TDX-01 (3m) and PorapakQ-S (3m) are used for respectively detecting CO, CO
2, H
2, CH
4, N
2
Biomass charcoal powder is adjusted coarse biometric oil reformation synthetic gas under the effect of catalyzer and electric current detailed process is: the 18%NiO-Al that at first with biomass charcoal powder, mass ratio is 1: 1
2O
3Carry out by a certain percentage ground and mixed with HZSM-5 mixed catalyst, kaolin and obtain mixed powder, with above-mentioned mixed powder under the condition of 100 ℃ of temperature dry 10 hours, sieving obtained biomass charcoal powder and the catalyst mixture finished product that particle diameter is 0.25mm-0.38mm; Described biomass charcoal powder and catalyst mixture are filled in built-in electric stove wire again and contact on every side and with the electric stove wire surface uniform, 500 ℃ were reduced 1 hour under High Purity Hydrogen, then connected preheating zone heat tape power supply, made the temperature of preheating zone in 180 ℃-200 ℃; Connect the power supply of the Ni-Cr electric stove wire that is used for interior heating, make the electric current that passes into the Ni-Cr electric stove wire be fixed on I=2.0A-4.0A, by the power of conditioned reaction device externally heated oven, the temperature in the reforming reactor inner chamber is regulated in 400 ℃ of-800 ℃ of scopes; Raw material coarse biometric oil reformation synthetic gas is passed in the barrel reactor inlet pipe preheating zone, enter after the preheating in the barrel reactor, make carbonic acid gas and biomass charcoal powder in the coarse biometric oil reformation synthetic gas issue soft coal solid/liquid/gas reactions and reverse water-gas reaction at catalyzer and galvanic action; Reacted mixed gas is obtained biological oil reforming-adjustment synthetic gas after through the tail gas collection system that comprises condenser, moisture eliminator.Wherein, catalyzer and biomass charcoal powder mass ratio are 0.8, and kaolin accounts for the 5wt% of total mixed powder quality, and electric current is 2.0A and 4.0A, and reaction pressure is normal pressure (1.1atm), and the reaction flow velocity is 60ml/min.
Table 3 has provided the effect of utilizing biomass charcoal powder to adjust coarse biometric oil reformation synthetic gas under the effect of catalyzer and electric current.Can find out from this table: when 600 ℃ of electric currents of temperature of reaction are 4A, CO in the reactant synthetic gas
2Transformation efficiency is that 82.1%, CO productive rate is 1.43mol CO/mol CO
2, can make rich CO
2Coarse biometric oil reformation synthetic gas ([CO
2Vol%] with [CO vol%] than being 6.33) effectively be converted into the biological oil reforming of rich CO-adjustment synthetic gas ([CO
2Vol%] with [CO vol%] than being 0.11).The result of table 3 with table 2 relatively can be found out, under identical temperature of reaction, when adjusting coarse biometric oil reformation synthetic gas with biomass charcoal powder under catalyzer and electric current acting in conjunction, its synthetic gas regulated efficiency (carbon dioxide component is converted into the efficient of carbon monoxide component in the synthetic gas) will be higher than the regulated efficiency of only adjusting coarse biometric oil reformation synthetic gas with biomass charcoal powder under catalyst action.
Table 3 biomass charcoal powder is adjusted the effect of coarse biometric oil reformation synthetic gas under the effect of catalyzer and electric current
Embodiment 3:
Adopt biological oil reforming-adjustment synthetic gas preparing biomass-based methanol.
In the present embodiment process, coarse biometric oil reformation synthetic gas adopts series fluidized bed apparatus system (patent: CN200910116098.6), in the prime fluidized-bed reactor, be biological oil vapour with biomass cracking at first under the water vapour atmosphere condition, then in the rear class fluidized-bed reactor, the organism in the bio oil steam is restructured as hydrogen and carbonic acid gas, main component and the content of coarse biometric oil reformation synthetic gas of making waste of the wood chip powder is as shown in table 4, it is characterized in that Fu Qing and carbon dioxide enriched synthetic gas (H
2/ CO=16.73, CO
2/ CO=6.33).In the present embodiment process, coarse biometric oil reformation synthetic gas is adjusted, the employing mass ratio is 1: 1 18%NiO-Al in the adjustment process
2O
3Identical with embodiment 2 with method with HZSM-5 (Si:Al=25) mixed catalyst, biomass charcoal powder, biological oil reforming synthetic gas Adjustment System.Be 600 ℃ in temperature of reaction, to pass into the catalytic bed electric current be that 4A, pressure are that 1atm and catalyzer and biomass charcoal powder mass ratio are that main component and the content of the biological oil reforming that obtains under 0.8 the adjustment reaction conditions-adjustment synthetic gas is as shown in table 4, it is characterized in that Fu Qing and CO rich synthesis gas (H
2/ CO=1.60, CO/CO
2=7.04).Two kinds of biological oil reforming synthetic gas shown in the table 4 (coarse biometric oil reformation synthetic gas and biological oil reforming-adjustment synthetic gas) are respectively as the reactant of preparing biomass-based methanol in the present embodiment.
Main component and the content of table 4 Biomass Syngas raw material
In the present embodiment process, the synthetic catalyst of use is CuZnAl catalyst, and its composition comprises 60wt%CuO, 30wt%ZnO and 10wt%Al
2O
3Biomass-based methanol synthesizes and estimates and carry out in continuous flow fixed catalytic bed reactor-gas-chromatography combined system: it comprises a tubular stainless steel high-pressure reactor (internal diameter: Φ 8mm, length: 40cm) and the reactant (Biomass Syngas) that is connected to both ends pass into pipeline and reaction end gas output channel, and be respectively equipped with control valve and reactant flow amount controller, tubular stainless steel high-pressure reactor is heated by outer electric furnace, and the access tube pipeline outer wall is provided with the external heating device for preheating; At first pass through condenser and moisture eliminator from the reaction end gas of reactor outlet discharging, uncondensable tail gas is taken a sample by the gas-chromatography six-way valve, unite with the TCD of GC-6890 gas chromatograph and FID and to do on-line analysis, two chromatographic column TDX-01 (3m) and PorapakQ-S (3m) are used for respectively detecting CO, CO
2, H
2, CH
4, N
2, and C
1-C
4Gaseous hydrocarbons; Condensable product takes the method for salt ice cooling to collect drainer, and the liquid product of collection adopts the SE30 capillary chromatographic column to make off-line analysis.It is that 5MPa and air speed are 10000h that biomass-based methanol synthesizes at 220 ℃-300 ℃ of temperature of reaction, pressure
-1Test under the synthetic reaction condition; The consumption of each building-up reactions CuZnAl catalyzer is 1g～2g; Before the building-up reactions, the CuZnAl catalyzer is at 10%vol hydrogen reducing atmosphere (flow velocity: reductase 12 0h 100ml/min) and under certain temperature programming (temperature rise rate: 2 ℃/min, final temperature: 240 ℃) condition; Reduction cools to room temperature after finishing, reducing atmosphere is switched importing be coarse biometric oil reformation synthetic gas or biological oil reforming-adjustment synthetic gas, the conditioned reaction condition is to temperature, air speed and the force value of above-mentioned appointment, carry out experiment and the product analysis of synthetic gas biomass-based methanol processed, reaction-ure conversion-age is calculated by the concentration before and after the reaction, and the selectivity of the carbonaceous products such as alcohol and space-time yield are taked marker method and calculated (document: Applied catalysis A:General 340 (2008) 87-97) in conjunction with C base normalization method.
Table 5 and table 6 have provided the effect of utilizing respectively coarse biometric oil reformation synthetic gas and biological oil reforming-adjustment synthetic gas preparing biomass-based methanol.As can be seen from Table 5: when coarse biometric oil reformation synthetic gas and CuZnAl catalyst are adopted in reaction, be that 5.0MPa and air speed are 10000h at 260 ℃ of temperature of reaction, pressure
-1The time, efficiency of carbon conversion in the reactant synthetic gas (is pressed the CO+CO of actual consumption
2CO+CO in mole number and the reactant
2The ratio calculation of mole number) be 9.6%, methanol yield (by per hour every gram Catalyst Production methyl alcohol grams calculating) is 366mg/ (h g
Cat), methyl alcohol selectivity (transforming the ratio calculation of mole number by moles of methanol in the synthetic product and all carbonaceous products) is 96.7%.As can be seen from Table 6: when biological oil reforming-adjustment synthetic gas and CuZnAl catalyst are adopted in reaction, be that 5.0MPa and air speed are 10000h at 260 ℃ of temperature of reaction, pressure
-1The time, efficiency of carbon conversion is 23.7% in the reactant synthetic gas, methanol yield is 1320mg/ (h g
Cat), the methyl alcohol selectivity is 98.5%.This shows, utilize the inventive method that coarse biometric oil reformation synthetic gas is adjusted after, significantly improved productive rate and the transformation efficiency of biomass-based methanol, the biomass-based methanol of acquisition is without sulphur, methanol yield is higher, reaches the degree that can realize industrial applications.
Table 5 adopts the effect of coarse biometric oil reformation synthetic gas preparing biomass-based methanol
Table 6 adopts the effect of biological oil reforming-adjustment synthetic gas preparing biomass-based methanol
| 240 | 5.0 | 10 4 | 13.6 | 760 | 98.8 |
| 260 | 5.0 | 10 4 | 23.7 | 1320 | 98.5 |
| 280 | 5.0 | 10 4 | 15.9 | 870 | 96.7 |
| 300 | 5.0 | 10 4 | 14.4 | 766 | 94.0 |
More than the method for preparing biomass-based methanol provided by the present invention is described in detail.Used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (12)
1. the method for a preparing biomass-based methanol is characterized in that, may further comprise the steps:
A) biomass cracking is generated bio oil steam and biomass charcoal powder;
B) described bio oil steam carries out steam reforming reaction after gas solid separation, gets coarse biometric oil reformation synthetic gas;
C) with described biomass charcoal powder, catalyzer and associating agent ground and mixed, the mixed powder that obtains is dry, under the hydrogen condition, reduce post-heating, pass into described coarse biometric oil reformation synthetic gas and carry out coal gas reaction and reverse water-gas reaction, the Mixed Gas Condensation that reaction is obtained, the dry synthetic gas of must biomass reforming-adjust;
D) described biomass are reformed-adjusted synthetic gas carries out building-up reactions, and the reaction end gas that obtains carries out condensation, obtains biomass-based methanol in the liquid product of collecting,
Described c) mass ratio of biomass charcoal powder and catalyzer is 1:0.5～1 in, and the mass percent that described associating agent accounts for described mixed powder is 3%～10%,
Described catalyzer is that mass parts is the NiO-Al of 1:0.8～1.2
2O
3Form with HZSM-5,
Described NiO-Al
2O
3Middle NiO accounts for NiO-Al
2O
3Mass percent be 17%～19%,
The mol ratio of silicon, aluminium is 25 among the described HZSM-5,
Described c) reaction is specially dried mixed powder is filled in the reactor, at High Purity Hydrogen, 490 ℃～510 ℃ lower reduction 55min～65min, after being heated to 400 ℃～800 ℃, coarse biometric oil reformation synthetic gas is issued soft coal solid/liquid/gas reactions and reverse water-gas reaction with biomass charcoal powder at catalyst action after 180 ℃～200 ℃ preheating.
2. method according to claim 1 is characterized in that, described a) middle biomass are one or more in stalk, wood chip or the rice husk.
3. method according to claim 1 is characterized in that, described associating agent is one or both in kaolin or the sesbania powder.
4. each described method in 3 according to claim 1 is characterized in that described c) in the mixed powder drying that obtains be specially at 100 ℃～120 ℃ lower dry 9h～11h.
5. method according to claim 4 is characterized in that, also sieves after the described mixed powder drying, and the mixed powder that sieves out particle diameter and be 0.25mm～0.38mm reduces.
6. method according to claim 5, it is characterized in that, described c) reaction is specially dried mixed powder is filled in the reactor of built-in electric stove wire, and contact with the electric stove wire surface uniform, at the lower reduction of High Purity Hydrogen, 490 ℃～510 ℃ 55min～65min, be heated to that coarse biometric oil reformation synthetic gas issues soft coal solid/liquid/gas reactions and reverse water-gas reaction with biomass charcoal powder at catalyzer and galvanic action after 400 ℃～800 ℃ after 180 ℃～200 ℃ preheating.
7. method according to claim 6 is characterized in that, described built-in electric stove wire is selected Ni-Cr electric stove wire or Fe-Cr-Ar electric stove wire.
8. method according to claim 6 is characterized in that, the electric current of described electric stove wire is 2.0A～4.0A.
9. according to claim 1, each described method in 6～8, it is characterized in that the reaction pressure of described coal gas reaction and reverse water-gas reaction is 1atm～1.2atm, the reaction flow velocity is 40ml/min～100ml/min.
10. method according to claim 1, it is characterized in that, also add synthetic catalyst when carrying out building-up reactions described d), described synthetic catalyst is CuZnAl catalyst, and mass percent consists of: 55%～65%CuO, 25%～35%ZnO and 5%～15%Al
2O
3
11. method according to claim 10, it is characterized in that, before carrying out building-up reactions, described synthetic catalyst is 9%～11% in volume percent, flow velocity is to heat up under the hydrogen reducing atmosphere of 95ml/min～105ml/min, and temperature rise rate is 2 ℃/min～3 ℃/min, is warming up to 235 ℃～245 ℃, keep 17h～19h, then be down to room temperature.
12. according to claim 10 or 11 described methods, it is characterized in that the temperature of described building-up reactions is 220 ℃～300 ℃, pressure is 4.5MPa～5.5MPa, and air speed is 9000h
-1～11000h
-1
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| CN107954831A (en) * | 2017-11-23 | 2018-04-24 | 莫祖勇 | A kind of method that biomass prepares methanol |
| CN107973697A (en) * | 2017-11-23 | 2018-05-01 | 莫祖勇 | A kind of method of preparing biomass-based methanol |
| CN108409530B (en) * | 2018-03-09 | 2021-02-19 | 吴辉胜 | Device and method for producing low-carbon mixed alcohol by using organic wastes |
| CN112795596B (en) * | 2021-01-29 | 2023-05-23 | 生帆 | Method for preparing hydrocarbon compound by using biomass material |
| CN113088342A (en) * | 2021-03-26 | 2021-07-09 | 叁久国际新能源科技有限公司 | Fuel replacing coal gas |
| CN115326971A (en) * | 2022-08-18 | 2022-11-11 | 中国核动力研究设计院 | Radioactive organic waste steam reforming tail gas analysis system |
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| CN101177239A (en) * | 2007-10-15 | 2008-05-14 | 中国科学技术大学 | Device and method for preparing hydrogen by the electrocatalysis water vapour recapitalization biological oil |
| CN101475143A (en) * | 2009-01-20 | 2009-07-08 | 中国科学技术大学 | Biomass hydrogen production in water vapour atmosphere and series fluidized bed apparatus system thereof |
| CN101519604A (en) * | 2009-01-24 | 2009-09-02 | 刘兴业 | Multilevel-control polyradical biomass-gasification energy regeneration system |
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| CN101177239A (en) * | 2007-10-15 | 2008-05-14 | 中国科学技术大学 | Device and method for preparing hydrogen by the electrocatalysis water vapour recapitalization biological oil |
| CN101654395A (en) * | 2008-08-20 | 2010-02-24 | 青岛生物能源与过程研究所 | Process and method thereof for preparing lower alcohol by biomass |
| CN101475143A (en) * | 2009-01-20 | 2009-07-08 | 中国科学技术大学 | Biomass hydrogen production in water vapour atmosphere and series fluidized bed apparatus system thereof |
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