CN107661781A - Biomass char oil-breaking catalyst and preparation method thereof - Google Patents
Biomass char oil-breaking catalyst and preparation method thereof Download PDFInfo
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- CN107661781A CN107661781A CN201711053107.2A CN201711053107A CN107661781A CN 107661781 A CN107661781 A CN 107661781A CN 201711053107 A CN201711053107 A CN 201711053107A CN 107661781 A CN107661781 A CN 107661781A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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Abstract
The present invention relates to a kind of biomass char oil-breaking catalyst and preparation method thereof, catalyst includes：Biomass semicoke, tar, chrome oxide green, cupric oxide, cesium hydroxide, lithium hydroxide, barium hydroxide, rubidium hydroxide, manganese dioxide, nickel oxide, sodium oxide molybdena, alumina adhesive.The present invention solves the Catalysts Deactivation Problems such as metal oxide and helper component separation aggregation, coking carbon distribution, realize recycling for biological semicoke class catalyst, higher gasification efficiency and the synthesis gas product of high-quality can be obtained at a lower temperature using biomass pyrolytic catalyst assisted microwave synthesis pyrolysis of gasified bio-matter, whole process does not introduce the exogenous gas consumption such as vapor, significantly reduces process energy consumption and production cost.
Description
Technical field
The invention belongs to energy-conserving and environment-protective technical fiel, and in particular to a kind of biomass char oil-breaking catalyst and its preparation
Method.
Background technology
Biomass pyrolysis for liquid production is in medium temperature (500-650 DEG C), the high rate of heat addition (104-105 DEG C/s) and extremely short gas
Under conditions of residence time (＜ 2s), biomass is directly pyrolyzed, product can make middle liquid product molecule exist through quick cooling
Further condensed before fracture generation gas, so as to obtain the bio liquid of high yield oil.But existing biomass cracking skill
Art common problem is the problem of catalyst is difficult to recycling, and in order to improve H2/CO, is consumed substantial amounts of
Vapor, increases energy consumption and gas consumption, process economy be not high.
The content of the invention
In view of the problems of prior art, the present invention provides a kind of biomass char oil-breaking catalyst.
In order to solve the above technical problems, technical scheme proposed by the present invention is as follows：A kind of biomass char oil-breaking catalysis
Agent, include the component of following parts by weight：The parts by weight of biomass semicoke 60~100, the parts by weight of tar 20~50, chrome oxide green 20~
30 parts by weight, the parts by weight of cupric oxide 15~20, the parts by weight of cesium hydroxide 10~20, the parts by weight of lithium hydroxide 8~16, barium hydroxide
8~16 parts by weight, the parts by weight of rubidium hydroxide 6~12, the parts by weight of manganese dioxide 5~10, the parts by weight of nickel oxide 1~5, sodium oxide molybdena 1
~5 parts by weight, the parts by weight of alumina adhesive 15~30.
According to biomass char oil-breaking catalyst provided by the invention and preparation method thereof, by biological semicoke, metal oxygen
Compound and the compound microwave-heating gasification for being prepared for biomass synthesis gas catalyst and being used for biomass of helper component, solve gold
Belong to the Catalysts Deactivation Problems such as oxide and helper component separation aggregation, coking carbon distribution, realize biological semicoke class catalyst
Recycle, can be obtained at a lower temperature using biomass pyrolytic catalyst assisted microwave synthesis pyrolysis of gasified bio-matter higher
The synthesis gas product of gasification efficiency and high-quality, whole process do not introduce the exogenous gas consumption such as vapor, significantly reduce work
Artistic skill consumes and production cost.
In addition, biomass char oil-breaking catalyst according to the above embodiment of the present invention, can also have following additional
Technical characteristic：
According to the example of the present invention, the biomass is the parts by weight of semicoke 60, and the tar is 20 parts by weight, described
Chrome oxide green is 20 parts by weight, and the cupric oxide is 15 parts by weight, and the cesium hydroxide is 10 parts by weight, and the lithium hydroxide is
8 parts by weight, the barium hydroxide are 8 parts by weight, and the rubidium hydroxide is 6 parts by weight, and the manganese dioxide is 5 parts by weight, institute
It is 1 parts by weight to state nickel oxide, and the sodium oxide molybdena is 1 parts by weight, and the alumina adhesive is 15 parts by weight.
According to the example of the present invention, the biomass is the parts by weight of semicoke 75, and the tar is 30 parts by weight, described
Chrome oxide green is 23 parts by weight, and the cupric oxide is 16 parts by weight, and the cesium hydroxide is 13 parts by weight, and the lithium hydroxide is
10 parts by weight, the barium hydroxide are 10 parts by weight, and the rubidium hydroxide is 8 parts by weight, and the manganese dioxide is 7 parts by weight,
The nickel oxide is 2 parts by weight, and the sodium oxide molybdena is 2 parts by weight, and the alumina adhesive is 20 parts by weight.
According to the example of the present invention, the biomass is the parts by weight of semicoke 90, and the tar is 40 parts by weight, described
Chrome oxide green is 26 parts by weight, and the cupric oxide is 18 parts by weight, and the cesium hydroxide is 16 parts by weight, and the lithium hydroxide is
12 parts by weight, the barium hydroxide are 13 parts by weight, and the rubidium hydroxide is 10 parts by weight, and the manganese dioxide is 8 parts by weight,
The nickel oxide is 3 parts by weight, and the sodium oxide molybdena is 3 parts by weight, and the alumina adhesive is 25 parts by weight.
According to the example of the present invention, the biomass is the parts by weight of semicoke 100, and the tar is 50 parts by weight, institute
It is 30 parts by weight to state chrome oxide green, and the cupric oxide is 20 parts by weight, and the cesium hydroxide is 20 parts by weight, the lithium hydroxide
For 16 parts by weight, the barium hydroxide is 16 parts by weight, and the rubidium hydroxide is 10 parts by weight, and the manganese dioxide is 10 weights
Part is measured, the nickel oxide is 5 parts by weight, and the sodium oxide molybdena is 5 parts by weight, and the alumina adhesive is 30 parts by weight.
In addition, present invention also offers a kind of preparation method of biomass char oil-breaking catalyst, comprise the following steps：
(1) biomass and the catalyst as described in claim any one of 1-5 are sent into microwave reactor and carry out pyrolytic gasification, obtain heat
Solve product；(2) thermal decomposition product obtains biomass synthesis gas and a small amount of liquid tar by purified treatment；(3) remained in reactor
Solid include catalyst and the newly-generated activated regeneration treatment of biological semicoke, recycle.
The advantages of above additional aspect, will be set forth in part in the description, and partly will become bright from the following description
It is aobvious, or recognized by the practice of the present invention.
Embodiment
Embodiment one
A kind of biomass char oil-breaking catalyst, include the component of following parts by weight：Biomass is the parts by weight of semicoke 60,
Tar is 20 parts by weight, and chrome oxide green is 20 parts by weight, and cupric oxide is 15 parts by weight, and cesium hydroxide is 10 parts by weight, hydroxide
Lithium is 8 parts by weight, and barium hydroxide is 8 parts by weight, and rubidium hydroxide is 6 parts by weight, and manganese dioxide is 5 parts by weight, and nickel oxide is 1 weight
Part is measured, sodium oxide molybdena is 1 parts by weight, and alumina adhesive is 15 parts by weight.
Embodiment two
A kind of biomass char oil-breaking catalyst, include the component of following parts by weight：Biomass is the parts by weight of semicoke 75,
Tar is 30 parts by weight, and chrome oxide green is 23 parts by weight, and cupric oxide is 16 parts by weight, and cesium hydroxide is 13 parts by weight, hydroxide
Lithium is 10 parts by weight, and barium hydroxide is 10 parts by weight, and rubidium hydroxide is 8 parts by weight, and manganese dioxide is 7 parts by weight, nickel oxide 2
Parts by weight, sodium oxide molybdena are 2 parts by weight, and alumina adhesive is 20 parts by weight.
Embodiment three
A kind of biomass char oil-breaking catalyst, include the component of following parts by weight：Biomass is the parts by weight of semicoke 90,
Tar is 40 parts by weight, and chrome oxide green is 26 parts by weight, and cupric oxide is 18 parts by weight, and cesium hydroxide is 16 parts by weight, hydroxide
Lithium is 12 parts by weight, and barium hydroxide is 13 parts by weight, and rubidium hydroxide is 10 parts by weight, and manganese dioxide is 8 parts by weight, and nickel oxide is
3 parts by weight, sodium oxide molybdena are 3 parts by weight, and alumina adhesive is 25 parts by weight.
Example IV
A kind of biomass char oil-breaking catalyst, include the component of following parts by weight：Biomass is the weight of semicoke 100
Part, tar is 50 parts by weight, and chrome oxide green is 30 parts by weight, and cupric oxide is 20 parts by weight, and cesium hydroxide is 20 parts by weight, hydrogen-oxygen
Change lithium is 16 parts by weight, and barium hydroxide is 16 parts by weight, and rubidium hydroxide is 10 parts by weight, and manganese dioxide is 10 parts by weight, oxidation
Nickel is 5 parts by weight, and sodium oxide molybdena is 5 parts by weight, and alumina adhesive is 30 parts by weight.
Comparative example one
Chrome oxide green and cupric oxide are not used, remaining composition is identical with embodiment one.
Comparative example two
Cesium hydroxide, lithium hydroxide, barium hydroxide, rubidium hydroxide are not used, and remaining composition is identical with embodiment one.
In addition, present invention also offers a kind of preparation method of biomass char oil-breaking catalyst, comprise the following steps：
(1) biomass and the catalyst as described in claim any one of 1-5 are sent into microwave reactor and carry out pyrolytic gasification, obtain heat
Solve product；(2) thermal decomposition product obtains biomass synthesis gas and a small amount of liquid tar by purified treatment；(3) remained in reactor
Solid include catalyst and the newly-generated activated regeneration treatment of biological semicoke, recycle.
Measure of merit
The gas of each embodiment and comparative example of biomass char oil-breaking catalyst by the present invention and preparation method thereof
Body yield, synthesis Gas content are compared.Test result such as following table：
Understood with reference to above-mentioned data, catalyst of the present invention, which is applied to biomass pyrogenation gasification process, can realize gas recovery ratio
Reach more than 90%, synthesis Gas content reaches more than 90%.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (6)
1. a kind of biomass char oil-breaking catalyst, it is characterised in that include the component of following parts by weight：Biomass semicoke 60
~100 parts by weight, the parts by weight of tar 20~50, the parts by weight of chrome oxide green 20~30, the parts by weight of cupric oxide 15~20, cesium hydroxide
10~20 parts by weight, the parts by weight of lithium hydroxide 8~16, the parts by weight of barium hydroxide 8~16, the parts by weight of rubidium hydroxide 6~12, dioxy
Change the parts by weight of manganese 5~10, the parts by weight of nickel oxide 1~5, the parts by weight of sodium oxide molybdena 1~5, the parts by weight of alumina adhesive 15~30.
2. biomass char oil-breaking catalyst according to claim 1, it is characterised in that the biomass is semicoke 60
Parts by weight, the tar are 20 parts by weight, and the chrome oxide green is 20 parts by weight, and the cupric oxide is 15 parts by weight, the hydrogen
Cesium oxide is 10 parts by weight, and the lithium hydroxide is 8 parts by weight, and the barium hydroxide is 8 parts by weight, and the rubidium hydroxide is 6
Parts by weight, the manganese dioxide are 5 parts by weight, and the nickel oxide is 1 parts by weight, and the sodium oxide molybdena is 1 parts by weight, the oxidation
Aluminium adhesive is 15 parts by weight.
3. biomass char oil-breaking catalyst according to claim 1, it is characterised in that the biomass is semicoke 75
Parts by weight, the tar are 30 parts by weight, and the chrome oxide green is 23 parts by weight, and the cupric oxide is 16 parts by weight, the hydrogen
Cesium oxide is 13 parts by weight, and the lithium hydroxide is 10 parts by weight, and the barium hydroxide is 10 parts by weight, and the rubidium hydroxide is
8 parts by weight, the manganese dioxide are 7 parts by weight, and the nickel oxide is 2 parts by weight, and the sodium oxide molybdena is 2 parts by weight, the oxygen
It is 20 parts by weight to change aluminium adhesive.
4. biomass char oil-breaking catalyst according to claim 1, it is characterised in that the biomass is semicoke 90
Parts by weight, the tar are 40 parts by weight, and the chrome oxide green is 26 parts by weight, and the cupric oxide is 18 parts by weight, the hydrogen
Cesium oxide is 16 parts by weight, and the lithium hydroxide is 12 parts by weight, and the barium hydroxide is 13 parts by weight, and the rubidium hydroxide is
10 parts by weight, the manganese dioxide are 8 parts by weight, and the nickel oxide is 3 parts by weight, and the sodium oxide molybdena is 3 parts by weight, the oxygen
It is 25 parts by weight to change aluminium adhesive.
5. biomass char oil-breaking catalyst according to claim 1, it is characterised in that the biomass is semicoke
100 parts by weight, the tar are 50 parts by weight, and the chrome oxide green is 30 parts by weight, and the cupric oxide is 20 parts by weight, described
Cesium hydroxide is 20 parts by weight, and the lithium hydroxide is 16 parts by weight, and the barium hydroxide is 16 parts by weight, the rubidium hydroxide
For 10 parts by weight, the manganese dioxide is 10 parts by weight, and the nickel oxide is 5 parts by weight, and the sodium oxide molybdena is 5 parts by weight, institute
It is 30 parts by weight to state alumina adhesive.
A kind of 6. preparation method of biomass char oil-breaking catalyst according to claim 1, it is characterised in that including
Following steps：(1) biomass and the catalyst as described in claim any one of 1-5 are sent into microwave reactor and carry out pyrolysis gas
Change, obtain thermal decomposition product；(2) thermal decomposition product obtains biomass synthesis gas and a small amount of liquid tar by purified treatment；(3) react
The solid remained in device includes catalyst and the newly-generated activated regeneration treatment of biological semicoke, recycles.
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| CN201711053107.2A CN107661781A (en) | 2017-10-31 | 2017-10-31 | Biomass char oil-breaking catalyst and preparation method thereof |
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| CN201711053107.2A CN107661781A (en) | 2017-10-31 | 2017-10-31 | Biomass char oil-breaking catalyst and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876788A (en) * | 2019-03-15 | 2019-06-14 | 福州大学 | A kind of preparation method and applications of biomass activation char catalyst |
| CN110540857A (en) * | 2019-08-05 | 2019-12-06 | 北京联谊华海能源科技有限公司 | Method for preparing chemical raw material and liquid fuel from biomass |
| CN110540856A (en) * | 2019-08-05 | 2019-12-06 | 北京联谊华海能源科技有限公司 | method for preparing chemical raw material and liquid fuel from biomass |
| CN114289024A (en) * | 2022-01-11 | 2022-04-08 | 万华化学集团股份有限公司 | Maleic anhydride hydrogenation catalyst and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109876788A (en) * | 2019-03-15 | 2019-06-14 | 福州大学 | A kind of preparation method and applications of biomass activation char catalyst |
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| CN110540857B (en) * | 2019-08-05 | 2020-05-26 | 北京海国龙油能源科技有限公司 | Method for preparing chemical raw material and liquid fuel from biomass |
| CN114289024A (en) * | 2022-01-11 | 2022-04-08 | 万华化学集团股份有限公司 | Maleic anhydride hydrogenation catalyst and preparation method thereof |
| CN114289024B (en) * | 2022-01-11 | 2023-12-19 | 万华化学集团股份有限公司 | Maleic anhydride hydrogenation catalyst and preparation method thereof |
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