CN107189817A - The preparation method of stalk biomass methyl methanol syngas - Google Patents
The preparation method of stalk biomass methyl methanol syngas Download PDFInfo
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- CN107189817A CN107189817A CN201710253523.0A CN201710253523A CN107189817A CN 107189817 A CN107189817 A CN 107189817A CN 201710253523 A CN201710253523 A CN 201710253523A CN 107189817 A CN107189817 A CN 107189817A
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- stalk
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- methyl methanol
- methanol syngas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/20—Apparatus; Plants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the chemical gas producing technology field of biomass, and in particular to a kind of preparation method of stalk biomass methyl methanol syngas, comprise the following steps：（1）Prepared by stalk gas, dry crop material oxidation thermal cracking is generated into coal gas, after gained coal gas is purified again, and cooling obtains stalk gas；（2）Stalk gas is purified, and devulcanizer is first passed through after gained stalk gas is compressed, then is passed through decoking oxygen-eliminating device, and the stalk air pressure contracting obtained after purification is standby；（3）Prepared by methyl methanol syngas, in proportion by step（2）The stalk gas of gained after purification is mixed with hydrogen, the hydrogen-carbon ratio f values in mixed gas is reached 2.10~2.15, or hydrogen-carbon ratio M values reach 2.00~2.05, and the compression of gained mixed gas is placed at least two months, methyl methanol syngas is produced.The present invention can use the cheap agricultural crops stalk of enormous amount for raw material, prepare high heating value unstripped gas and synthesis gas, and further catalyze and synthesize biomass methanol.
Description
Technical field
The invention belongs to the chemical gas producing technology field of biomass, and in particular to a kind of stalk biomass methyl methanol syngas
Preparation method.
Background technology
Biomass chemistry gas processed is that a utilization thermally decomposes broken biological matter macromolecular organic structure（Main component is fiber
Plain cellulose, hemicellulose hemicellulose, lignin lignin）The process of small molecule burning mixture is produced,
The energy conversion process that i.e. biomass material is heated under anaerobic condition.The unstripped gas obtained after gasification product is purified can be made
It is used to produce boiler heat supplying for fuel gas, the different occasion such as gas turbine power generation, by means of specific technique, by gasification product
Being further converted to synthesis gas is used to produce the liquid fuels such as methanol, ethanol.
The heat chemistry gasification of biomass refers to by the use of the oxygen or oxygen carrier in air as gasifying agent, and biomass is big
Molecule（Main component is cellulose, hemicellulose, lignin etc.）The process of middle carbon hydrogen element oxidation generation fuel gas.Thermalization
Learning gasification includes high-temperature oxydation and reduction reaction, and solid biomass is dried and retort process.Biomass fast pyrogenation first
For unstripped gas（Such as H2、CO、CO2、CH4、C2H2、C2H4、C2H6Deng）And the product such as tar, coke, then through steam gasification or urge
Agent catalysis, Pintsch process purification, make the materials such as the tar in unstripped gas, coke be further converted to CO, H2, generation cleaning
Biomass synthesis gas（Main Ingredients and Appearance is：CO、H2、CO2, a small amount of CH4With micro C2Hydrocarbons）.
Biomass methanol technology is totally divided into two large divisions, and Part I is biomass heat chemistry vaporizing system unstripped gas
And synthesis gas；Part II be synthesis gas under certain pressure and temperature conditionss through catalyst synthetic coarse methanol, crude carbinol
Methanol product is obtained after rectifying.
Biomass thermal chemistry legal system methanol technology has carried out substantial amounts of experimental study since the eighties, to variety classes
The heat chemistry gasification of biomass and testing equipment and a large amount of tackling key problem researchs of technological process progress for catalyzing and synthesizing methanol, although biological
Matter methanol technical research has been achieved with remarkable progress, but still has many problem urgent need to resolve, is concentrated mainly on the following aspects：
（1）Biomass thermal chemical gasification and research on utilization such as are only limitted to prepare heating boiler, generate electricity, cook at the low heat value that uses
Gas sectional, medium calorific value gas production technology is only limitted to laboratory and small-scale pilot scale research stage, to further synthesizing methanol
Technical research be in blank.
（2）Gas component prepared by biomass thermal chemical gasification does not meet the requirement of methanol synthesis technology.Such as gas ingredients
Still belong to unstripped gas, do not reach gas composition requirement；H/C mol ratios do not reach methanol-fueled CLC theoretical proportions in synthesis gas；And
CO in synthesis gas2、CH4Content had a strong impact on the normal performance of catalyst performance.
（3）It is general that the biomass gasification equipment studied at present is tested different kind organism matter or mixing biomass material gasification
Property is not strong.
（4）The biomass material studied at present is generally the lignocellulosic biomass such as timber, sawdust and rice husk, peanut shell, corn
The hard materials such as core, the domestic a large amount of agricultural crop straws for being badly in need of solving are gasified the less of research, the especially gas of maize straw
Change research and application is less.
（5）The catalyst research of biomass thermal chemical gasification preparing synthetic gas is less, single varieties, and performance is general, synthesis gas
The catalyst research of catalysis methanol processed is in blank.
（6）The unstripped gas of the equipment for gasification production of current commercialization is only 4~6MJ/m3Low-BTU gas.
The content of the invention
In view of the above-mentioned problems, with reference to the current national conditions of China, i.e., a large amount of stalk biomass are cheap, and the present invention provides a kind of
The preparation method of stalk biomass methyl methanol syngas, can use the cheap agricultural wastes of enormous amount（Such as crop material）For
Raw material, prepares high heating value unstripped gas and synthesis gas, and further catalyzes and synthesizes biomass methanol.
To solve problem above, the present invention is achieved through the following technical solutions：
A kind of preparation method of stalk biomass methyl methanol syngas is designed, is comprised the following steps：
（1）It is prepared by stalk gas
By dry crop material（It is preferred that maize straw, is ground into the particle that length is 2~3cm）It is transported to biomass gasification equipment
（Oxicracking stove）In, stalk oxidation thermal cracking is generated coal gas, gained coal gas is purified again（Such as tar removing, dedusting）
Afterwards, cooling obtains stalk gas, stores for future use；
（2）Stalk gas is purified
Because, containing a certain amount of oxygen, tar, sulfide etc., wherein tar, sulfide and oxygen are serious in stalk gas
Catalyst is injured, causes catalyst to lose activity in methanol-fueled CLC workshop section, shortens its service life.So, in synthesizing methanol
Before, it is necessary to remove.
In addition, hydrogen content is relatively low in unstripped gas, theoretical according to chemical reaction, methyl methanol syngas requires that hydrogen-carbon ratio is more than 2.
Therefore, before synthesis, stalk gas need to be purified, including the technical finesse, system such as tar destruction, deoxidation, desulfurization, allotment hydrogen
It is standby to go out to meet the biomass straw high heating value synthesis gas of methanol-fueled CLC requirement.
Gained stalk air pressure is reduced to 3400~3600MPa, devulcanizer is first passed through, then be passed through decoking oxygen-eliminating device（Ring
Border pressure is 0.6MPa, and environment temperature is 795~805 DEG C）, the stalk air pressure obtained after purification contracts standby；The desulfurization
Device is tubular electric furnace, provided with desulfurization basket in its interlayer, the ZnO powder equipped with parcel cellucotton in the desulfurization basket；The decoking
Oxygen-eliminating device is tubular electric furnace, arranged in a crossed manner in its interlayer to have ZR types catalyst, activated carbon and thin copper wire；
（3）It is prepared by methyl methanol syngas
In proportion by step（2）The stalk gas of gained after purification is mixed with hydrogen, reaches the hydrogen-carbon ratio f values in mixed gas
Arrive（H2- CO2）/（CO+CO2）=2.10~2.15, or hydrogen-carbon ratio M values reach H2/（CO+1.5CO2）=2.0~2.05, by gained
Mixed gas is placed at least two months in 35~45 DEG C of sealings, produces methyl methanol syngas.
The present invention is with following positive beneficial technique effect：
（1）The present invention provides the high heating value synthesis gas for complying fully with methanol synthetizing technology requirement using gasifying stalk.
（2）The present invention devises the purification technique of stalk gas, especially zinc oxide desulfurization technology, is urged using ZR types
Agent, it is ensured that methyl methanol syngas after purification reaches theoretical standard.
（3）The present invention combines long-term practical studies, the feedstock hydrocarbon proportioning of scientific design methanol-fueled CLC.
Embodiment
Following embodiment facilitates a better understanding of the present invention, but does not limit the present invention.It is involved in following embodiment
And equipment, be then commercially available conventional equipment unless otherwise instructed, involved processing step, unless otherwise instructed, then
For Conventional process steps.
Embodiment 1：A kind of preparation method of stalk biomass methyl methanol syngas, comprises the following steps：
（1）It is prepared by stalk gas
By dry maize straw, the particle that length is 2~3cm is ground into, is transported in oxicracking stove, routine operation makes stalk
Oxidation thermal cracking generates coal gas, and gained coal gas is purified again（Tar removing, dedusting）Afterwards, cooling obtains stalk gas, stores up
Deposit standby；The chemical composition of gained stalk gas is shown in Table 1.
The stalk gas principal component analysis data of table 1
。
（2）Stalk gas is purified
The trace sulfide contained in stalk gas can cause catalyst poisoning, during using common copper-based catalysts, sulfur content
0.2ppm should be less than, if containing 1ppm, after being run through half a year, catalyst sulfur content will be up to 4~6%, no matter in unstripped gas
Sulphur exists with hydrogen sulfide or organic sulfur form, the metal active component in catalyst is produced metal sulfide and is lost
Activity.Sulfide can react the impurity such as generation mercaptan, sulphur dimethyl ether, have a strong impact on the quality of crude carbinol in reaction system；Separately
The metal oxide film of outer sulfide destruction consersion unit and pipeline, makes equipment pipe by carbon monoxide corrosion generation carbonyl iron, carbonyl
The compounds such as base nickel, make pipe-line equipment cause corrosion, its service life are reduced, therefore, it is necessary to remove.
Gained stalk air pressure is reduced to 3500Mpa, devulcanizer is first passed through, then be passed through decoking oxygen-eliminating device（Environmental pressure
For 0.6MPa, environment temperature is 800 ± 5 DEG C）, stalk gas after purification is obtained through the compression of G2V-5/200 diaphragm type compressors
To high-pressure cylinder, the unstripped gas prepared as synthesis gas is standby.The devulcanizer is 623-1.3 type tubular electric furnaces, in its interlayer
Provided with desulfurization basket, the ZnO powder of parcel cellucotton is housed in the desulfurization basket；The decoking oxygen-eliminating device is 623-1.3 type tubuloses
It is arranged in a crossed manner in electric furnace, its interlayer to have ZR types catalyst, activated carbon and thin copper wire.
The shortcomings of during in view of dry, larger wet desulphurization expense, operating cost；This example employs zinc oxide desulfurization, occurs
Chemical reaction be：
Gas after purification is tested through analysis：Sulfide content is not more than 0.0012ppm, and oxygen and tar are not detected by, complete
Meet methanol high heating value synthesis gas standard entirely.
（3）It is prepared by methyl methanol syngas
Due to there is carbon monoxide, carbon dioxide and hydrogen simultaneously in stalk gas, so, under suitable catalytic condition,
The reaction system occur synthetic reaction be：
。
The first standby hydrogen of injection institute in empty high-pressure cylinder, then stalk gas after purification pressed into f values with compressor
2.12, which calculate ratio press-in steel cylinder, places at least two months, produces methyl methanol syngas, its constituent analysis is shown in Table 2.
The cornstalk syngas elemental analysis data of table 2
。
Embodiment 2：A kind of preparation method of stalk biomass methyl methanol syngas, comprises the following steps：
（1）It is prepared by stalk gas
By dry maize straw, the particle that length is 2~3cm is ground into, is transported in oxicracking stove, routine operation makes stalk
Oxidation thermal cracking generates coal gas, and gained coal gas is purified again（Tar removing, dedusting）Afterwards, cooling obtains stalk gas, stores up
Deposit standby；
（2）Stalk gas is purified
Gained stalk air pressure is reduced to 3500Mpa, devulcanizer is first passed through, then be passed through decoking oxygen-eliminating device（Environmental pressure is
0.6MPa, environment temperature is 800 ± 5 DEG C）, the stalk gas obtained after purification is compressed to through G2V-5/200 diaphragm type compressors
High-pressure cylinder, the unstripped gas prepared as synthesis gas is standby.The devulcanizer is 623-1.3 type tubular electric furnaces, is set in its interlayer
There is the ZnO powder equipped with parcel cellucotton in desulfurization basket, the desulfurization basket；The decoking oxygen-eliminating device is 623-1.3 types tubulose electricity
It is arranged in a crossed manner in stove, its interlayer to have ZR types catalyst, activated carbon and thin copper wire.
（3）It is prepared by methyl methanol syngas
The first standby hydrogen of injection institute in empty high-pressure cylinder, then it is 2.02 that stalk gas after purification is pressed into M values with compressor
Ratio press-in steel cylinder after place at least two months, produce methyl methanol syngas.
Claims (7)
1. a kind of preparation method of stalk biomass methyl methanol syngas, it is characterised in that comprise the following steps：
（1）It is prepared by stalk gas
Dry crop material is transported to oxidation thermal cracking in biomass gasification equipment and generates coal gas, gained coal gas is carried out again net
Change, then cooling obtains stalk gas, stores for future use；
（2）Stalk gas is purified
Gained stalk air pressure is reduced to 3400~3600Mpa, devulcanizer is then passed to, then is passed through decoking oxygen-eliminating device, is obtained
Stalk air pressure contracting after purification is standby；
（3）It is prepared by methyl methanol syngas
In proportion by the step（2）The stalk gas of middle gained after purification is mixed with hydrogen, makes the hydrogen carbon in mixed gas
Reached than f values（H2- CO2）/（CO+CO2）=2.10~2.15, or hydrogen-carbon ratio M values reach H2/（CO+1.5CO2）=2.00~
2.05, gained mixed gas is placed at least two months in sealing at 35~45 DEG C, methyl methanol syngas is produced.
2. the preparation method of stalk biomass methyl methanol syngas according to claim 1, it is characterised in that：In step（1）
Described in crop material be maize straw, be 2~3cm of length stalk particle.
3. the preparation method of stalk biomass methyl methanol syngas according to claim 1, it is characterised in that：In step（1）
Described in purifying step include tar removing, dedusting.
4. the preparation method of stalk biomass methyl methanol syngas according to claim 1, it is characterised in that：In step（2）
In, the devulcanizer is tubular electric furnace, provided with desulfurization basket in its interlayer, the ZnO powder equipped with parcel cellucotton in the desulfurization basket
End.
5. the preparation method of stalk biomass methyl methanol syngas according to claim 1, it is characterised in that：In step（2）
In, the decoking oxygen-eliminating device is tubular electric furnace, arranged in a crossed manner in its interlayer to have ZR types catalyst, activated carbon and thin copper wire.
6. the preparation method of stalk biomass methyl methanol syngas according to claim 5, it is characterised in that：The ZR types are urged
Agent is dolomite dust.
7. the preparation method of stalk biomass methyl methanol syngas according to claim 1, it is characterised in that：In step（2）
In, the environmental pressure in the decoking oxygen-eliminating device is 0.6MPa, and environment temperature is 795~805 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710253523.0A CN107189817A (en) | 2017-04-18 | 2017-04-18 | The preparation method of stalk biomass methyl methanol syngas |
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| CN201710253523.0A CN107189817A (en) | 2017-04-18 | 2017-04-18 | The preparation method of stalk biomass methyl methanol syngas |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114214092A (en) * | 2022-02-23 | 2022-03-22 | 天津骐讯科技有限公司 | Process and device for producing methanol by biomass gasification |
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| WO2008067627A2 (en) * | 2006-12-05 | 2008-06-12 | Braskem S.A. | A method for the production of one or more olefins, an olefin, and a polymer |
| CN101598039A (en) * | 2009-06-22 | 2009-12-09 | 郑州金土地能源科技有限公司 | Solar energy-biomass energy-Hydrogen Energy coupling and complementing electricity-generating method |
| CN101913558A (en) * | 2010-08-02 | 2010-12-15 | 黑龙江建龙钢铁有限公司 | Method for preparing methanol synthesis gas from hydrogen extracted from methanol releasing gas and coke oven gas and converter gas |
| CN105585426A (en) * | 2016-01-15 | 2016-05-18 | 嘉善中环生物质能源有限公司 | Method and device for synthesizing methanol from straw through oxygen control pyrolysis |
-
2017
- 2017-04-18 CN CN201710253523.0A patent/CN107189817A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008067627A2 (en) * | 2006-12-05 | 2008-06-12 | Braskem S.A. | A method for the production of one or more olefins, an olefin, and a polymer |
| CN101195775A (en) * | 2007-08-17 | 2008-06-11 | 内蒙古金骄特种新材料有限公司 | Biological mixed alcohol and preparation method thereof |
| CN101598039A (en) * | 2009-06-22 | 2009-12-09 | 郑州金土地能源科技有限公司 | Solar energy-biomass energy-Hydrogen Energy coupling and complementing electricity-generating method |
| CN101913558A (en) * | 2010-08-02 | 2010-12-15 | 黑龙江建龙钢铁有限公司 | Method for preparing methanol synthesis gas from hydrogen extracted from methanol releasing gas and coke oven gas and converter gas |
| CN105585426A (en) * | 2016-01-15 | 2016-05-18 | 嘉善中环生物质能源有限公司 | Method and device for synthesizing methanol from straw through oxygen control pyrolysis |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114214092A (en) * | 2022-02-23 | 2022-03-22 | 天津骐讯科技有限公司 | Process and device for producing methanol by biomass gasification |
| CN114214092B (en) * | 2022-02-23 | 2022-05-03 | 天津骐讯科技有限公司 | Process and device for producing methanol by biomass gasification |
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