CN115970694A - Preparation of biomass-based catalyst and application of biomass-based catalyst in process of preparing synthesis gas from methanol steam - Google Patents
Preparation of biomass-based catalyst and application of biomass-based catalyst in process of preparing synthesis gas from methanol steam Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 234
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000002028 Biomass Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 title abstract description 39
- 238000003786 synthesis reaction Methods 0.000 title abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 16
- 239000003610 charcoal Substances 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 238000002309 gasification Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000003889 chemical engineering Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 2
- 238000010000 carbonizing Methods 0.000 claims 1
- 230000008016 vaporization Effects 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 235000001759 Citrus maxima Nutrition 0.000 description 5
- 244000276331 Citrus maxima Species 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229920002522 Wood fibre Polymers 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002025 wood fiber Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- XXLDWSKFRBJLMX-UHFFFAOYSA-N carbon dioxide;carbon monoxide Chemical compound O=[C].O=C=O XXLDWSKFRBJLMX-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
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- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
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- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
The invention belongs to the field of catalysts of industrial synthesis gas and production processes thereof, and provides preparation of a biomass-based catalyst and application of the biomass-based catalyst in a process for preparing synthesis gas from methanol steam, which are divided into preparation of a renewable biomass-based catalyst and design and application of a process for preparing synthesis gas from methanol steam. The preparation of the renewable biomass-based catalyst mainly comprises the steps of biomass pretreatment, biomass charcoal particle preparation, active component (copper and cobalt) loading and catalyst forming; the process for preparing the synthesis gas by the methanol steam mainly comprises the steps of pretreatment of a catalyst, feeding of a methanol water solution, catalytic reaction, a condensing device and gas outlet. The invention prepares the renewable biomass-based catalyst, and applies the renewable biomass-based catalyst to the production process of preparing the synthesis gas from the methanol steam with simpler process and less energy consumption to form a complete system for preparing the synthesis gas from the methanol steam, thereby achieving the purposes of reducing the production cost of the catalyst for preparing the synthesis gas from the methanol steam, utilizing the waste biomass, simplifying the process and reducing the energy consumption.
Description
Technical Field
The invention belongs to the field of catalysts of industrial synthesis gas and production processes thereof, and particularly relates to a preparation method of a biomass-based catalyst and application of the biomass-based catalyst in a process for preparing synthesis gas from methanol steam.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The industrial synthesis gas consists of carbon monoxide and hydrogen, is a common chemical raw material gas, is commonly used for industrial ammonia synthesis, fischer-Tropsch synthesis, hydroformylation and the like, and has large demand and wide application. The existing industrial production of synthesis gas is mainly prepared from fossil fuels such as coal, petroleum, natural gas and the like at high temperature, and has the disadvantages of reduced raw material reserves, more complex process and high energy consumption.
The preparation of the methanol can be catalyzed by biomass, chinese patent documents CN107189817A, CN101863736A and the like disclose methods for preparing the methanol by the biomass, and prove that the methanol can be prepared from the biomass, belongs to renewable energy sources, has wide sources and low price, so the methanol can be used as a reaction raw material of synthesis gas. However, the process of preparing the synthesis gas by using the methanol belongs to a high-energy-consumption unsteady system, and a catalyst is required to be added to promote the reaction to be efficiently and stably carried out with low energy consumption.
The catalyst is generally composed of a support and an active species. The conventional catalyst carrier for preparing the synthetic gas by using the methanol is a metal oxide or a ceramic material, and the preparation process of the metal oxide carrier needs to extract a metal compound from related metal ores and then prepare the catalyst by a precipitation method or a sol-gel method; the preparation of the ceramic material needs to be realized at a high temperature of more than 1000 ℃, and the preparation process is complicated. Therefore, the use of metal oxide or ceramic material as the carrier of the catalyst has the disadvantages of occupying metal resources, high cost and large energy consumption.
Research shows that the catalyst with fibrous structure has the features of high mechanical strength, great porosity and great surface area. The xylem of the biomass contains a large amount of wood fibers, the wood fibers have natural fibers and a single-grain pore structure, so that the biomass catalytic cracking catalyst has great advantages in uniform distribution of active components and adsorption of reaction raw materials, and is favorable for full reaction in the field of catalysis.
Chinese patent document CN109364922A discloses a high-load nano metal catalyst of a biomass carbon-based material, and a preparation method and application thereof. Removing yellow peel from the shaddock peel, freeze-drying for 2-3 days, and grinding to powder to obtain shaddock peel powder; rapidly adding the shaddock peel powder into a nitrate solution under stirring, and stirring at 50 ℃ until the shaddock peel powder is dried; then drying for 12h at 100 ℃, and then obtaining the precursor of the catalyst by high-temperature roasting. In the preparation process of the catalyst, peeling is complex, the freeze drying period is long, and the shaddock peel powder and nitrate are stirred to be dry under the stirring state, so that energy consumption is high, and the period is long; in addition, the powdered catalyst needs to be compacted in industry, but the compaction can reduce the effective catalytic area of the catalyst for reaction, reduce the reaction efficiency while increasing the equipment cost and energy consumption, and is not beneficial to industrialization.
Researches find that the reaction formula of the synthesis gas prepared by directly cracking the methanol is shown as the formula 1.1, the synthesis gas is directly generated from the methanol in the reaction, the reaction temperature needs to reach 310 +/-10 ℃ under the participation of a catalyst, and the energy consumption is higher; after water is added into a reaction raw material methanol, in a reaction system for preparing synthesis gas from a methanol water solution, the reaction process is mainly realized by two steps of a formula 1.2 and a formula 1.3, and can be realized at a lower temperature under the participation of a catalyst, and the energy consumption is lower compared with the energy consumption of direct cracking of methanol.
CH 3 OH→2H 2 +CO ΔH 298K ＝90.8KJ/mol 1.1
CH 3 OH+H 2 O→3H 2 +CO 2 ΔH 298K ＝49.4KJ/mol 1.2
H 2 +CO 2 →CO+H 2 O ΔH 298K ＝41.19KJ/mol 1.3
Chinese patent document CN105460889A discloses a process for producing a synthetic gas fuel from methanol, which comprises the steps of changing a methanol liquid raw material into a gaseous state, heating the gaseous state by a heat exchanger, further heating the gaseous state to 310 ± 10 ℃ by a superheater, and then reacting the gaseous state in a reactor. The reaction process is relatively complicated for gasification preheating treatment before reaction, and has high reaction temperature and large energy consumption.
Disclosure of Invention
The invention aims to overcome the defects that the conventional metal oxide carrier catalyst occupies metal resources, has high preparation cost and complex process, the existing biomass carbon-based catalyst has complex preparation process, long period and high energy consumption, the powdered catalyst has certain limitation on the flow rate of reactants and is not beneficial to industrialization, and the defects of complex preheating process, high reaction temperature and high energy consumption in the process of preparing synthesis gas from methanol; the waste biomass with high wood fiber content is utilized, the biomass is pretreated by simple processes with low energy consumption and simplicity, such as drying, crushing, heat treatment and the like, and the large-size fibrous renewable biomass-based catalyst is prepared by a simple dipping roasting method and is applied to a production process for preparing synthesis gas from methanol steam with simple process and low energy consumption to form a perfect system for preparing synthesis gas from methanol steam, so that the aims of reducing the production cost of the catalyst for preparing synthesis gas from methanol steam, utilizing the waste biomass, simplifying the process and reducing the energy consumption are fulfilled, and a basis is provided for the industrialization of preparing synthesis gas from methanol.
The system for preparing the synthesis gas from the methanol steam is divided into the preparation of a renewable biomass-based catalyst and the design and application of a process for preparing the synthesis gas from the methanol steam. The preparation of the renewable biomass-based catalyst mainly comprises the steps of pretreatment of biomass, preparation of biomass charcoal particles, loading of active components (copper and cobalt) and forming of the catalyst; the process for preparing the synthesis gas by using the methanol steam mainly comprises the steps of pretreatment of a catalyst, feeding of a methanol water solution, catalytic reaction, a condensing device and gas outlet.
In order to achieve the purpose, the invention adopts the following technical scheme:
preparation of a biomass-based catalyst and application thereof in a process for preparing synthesis gas from methanol steam, comprising the following steps:
A. selecting waste biomass, drying the waste biomass at 90-110 ℃ to remove excessive moisture, and crushing the waste biomass into 2-30 meshes to form granular and fibrous biomass crushed materials;
B. placing the biomass crushed material in an inert atmosphere flowing at 450-650 ℃ for 1-2h, and removing ash, moisture and organic matters to obtain biomass charcoal particles;
C. weighing nitrate solids of copper and cobalt in a certain mass ratio of 1-5;
D. weighing biochar particles, wherein the mass of the biochar particles is 1-10 times of the sum of the mass of a copper element and the mass of a cobalt element, and placing the biochar particles in a copper-cobalt mixed solution to form a copper-cobalt/carbon mixture;
E. ultrasonically cleaning the copper-cobalt/carbon mixture at 40-90 ℃ for 10-20min, further placing the mixture into a magnetic stirrer at 40-90 ℃ for uniform stirring for 20-40min, then aging the mixture at 40-90 ℃ for 6-12h, and fully evaporating the water in the mixture at 100-120 ℃ to obtain a biomass-based catalyst precursor loaded with copper and cobalt elements;
F. placing the biomass-based catalyst precursor loaded with the copper and cobalt elements in a nitrogen atmosphere with the flow rate of 20-50ml/min, and roasting for 1.5-3.5h at the temperature of 300-450 ℃ to obtain a copper and cobalt/carbon catalyst;
G. loading the copper cobalt/carbon catalyst into a catalytic reactor at 5-50% 2 /N 2 Reducing for 2-4h at 240-260 ℃ in atmosphere;
H. selecting methanol and water as raw materials;
I. methanol and water are mixed in a molar ratio of 1:1-1:5, fully mixing the components to form a methanol aqueous solution, conveying the methanol aqueous solution into a gasification chamber by using a pressure pump, and converting the methanol aqueous solution into methanol and water vapor under the condition that the temperature is 100-130 ℃;
J. introducing the mixed gas of methanol and water vapor into a reactor filled with 0.1-0.5g of copper-cobalt/biochar catalyst, and generating carbon monoxide and hydrogen at the temperature of 220-280 ℃;
K. the generated carbon monoxide, hydrogen, unreacted methanol gas and water vapor flow through a condensing device, gaseous methanol and gaseous water are condensed into liquid, and the liquid flows back to a gasification chamber for re-reaction, and the resultant synthetic gas can directly enter other chemical engineering procedures through a separating device;
the patent technology of the invention has the advantages that:
1) The method for preparing the synthesis gas by preparing the catalyst from the waste biomass and catalyzing the methanol steam is a renewable innovative green process route, and realizes the recycling of biomass resources.
2) The biomass absorbs carbon dioxide in the nature through photosynthesis, and the process converts the carbon dioxide in the air into industrial raw material carbon monoxide for utilization.
3) The production process of the biomass-based catalyst provided by the invention is simple in flow, wide in raw material source, low in cost, universal, easy to industrialize and has potential market value.
4) The process for preparing the synthesis gas from the methanol steam provided by the invention is simple, low in energy consumption and high in synthesis gas purity, and has potential commercial value.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic process diagram of a methanol steam to syngas system according to one embodiment of the invention.
FIG. 2 is a scanning electron microscope and a projection electron microscope image of a fibrous catalyst, wherein a is a scanning electron microscope image of a catalyst; and b is a transmission electron microscope picture of the catalyst.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value determined, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The system for preparing the synthesis gas from the methanol steam is divided into the preparation of a renewable biomass-based catalyst and the design and application of a process for preparing the synthesis gas from the methanol steam. The preparation of the renewable biomass-based catalyst mainly comprises the steps of biomass pretreatment, biomass charcoal particle preparation, active component (copper and cobalt) loading and catalyst forming; the process for preparing the synthesis gas by the methanol steam mainly comprises the steps of pretreatment of a catalyst, feeding of a methanol water solution, catalytic reaction, a condensing device and gas outlet.
In the present invention, the pretreatment step of biomass is generally divided into drying and crushing, wherein the temperature of drying is preferably 90 to 110 ℃, and the degree of crushing is preferably 2 to 30 mesh.
In the invention, the preparation step of the biomass charcoal particles is generally high-temperature pyrolysis carbonization in an inert atmosphere, the inert atmosphere is preferably a nitrogen atmosphere, and the carbonization temperature is preferably 450-650 ℃.
In the invention, the active components (copper and cobalt) are loaded by an impregnation method, the atomic ratio of copper to cobalt is preferably 1-5.
In the present invention, the catalyst is formed by a roasting method, wherein the roasting atmosphere is preferably nitrogen atmosphere, the roasting temperature is preferably 300-450 ℃, and the roasting time is preferably 1.5-3.5h.
In the present invention, the pretreatment of the catalyst is usually carried out by a hydrogen reduction method, wherein the reducing gas is preferably 5-50% by volume H 2 /N 2 The temperature of the reduction is preferably 240-260 ℃ and the time of the reduction is preferably 2-4h.
In the invention, the methanol aqueous solution is gasified by a pressure pump and then injected into a reactor, wherein the molar ratio of methanol to water is preferably 1:1-1:5, the gasification temperature is preferably 100 to 130 ℃.
In the invention, the catalytic reaction is carried out in a reactor filled with a copper-cobalt/biochar catalyst, wherein the loading amount of the catalyst is preferably 0.1-0.5g, and the reaction temperature is preferably 220-280 ℃.
In the invention, the condensing device usually adopts a water condensing device, and the condensed solution flows back to the gasification chamber to participate in the reaction again.
In the present invention, the temperature of the hydrogen and carbon monoxide produced is generally in the range of 15 to 30 ℃ and the pressure is generally atmospheric.
The process and method of the present invention are particularly suitable for the synthesis gas production from methanol steam, and may further comprise separation and purification steps and units for further separation and purification of the produced gas (hydrogen, carbon monoxide and a small amount of carbon dioxide), which are not described in detail herein.
The present invention will be described in detail below by way of examples. In the following examples, the gas produced was analyzed by gas chromatography using ceriran 436C.
Example 1:
a) Selecting disposable chopsticks as raw materials, drying the disposable chopsticks at 100 ℃ to remove redundant moisture, and crushing the disposable chopsticks to 10 meshes to form granular and fibrous biomass crushed materials;
b) Placing the biomass crushed material in a nitrogen atmosphere at 550 ℃ for 1.5h, and removing ash, moisture and organic matters to obtain biomass charcoal particles;
c) Weighing 0.1789g of copper nitrate trihydrate and 0.3209g of cobalt nitrate hexahydrate solid, and adding deionized water to fully dissolve the copper nitrate trihydrate and the cobalt nitrate hexahydrate to form a copper-cobalt mixed solution;
d) Weighing 0.6035g of biochar particles, and placing the biochar particles into a copper-cobalt mixed solution to form a copper-cobalt/carbon mixture;
e) Ultrasonically cleaning a copper-cobalt/carbon mixture at 50 ℃ for 10min, magnetically stirring at 50 ℃ for 20min, aging at 50 ℃ for 8h, and fully evaporating water in the mixture at 110 ℃ to obtain a biomass-based catalyst precursor loaded with copper and cobalt elements;
f) Placing the biomass-based catalyst precursor loaded with the copper-cobalt element in a nitrogen atmosphere with the flow rate of 25ml/min, and roasting for 2 hours at the temperature of 350 ℃ to obtain a copper-cobalt/carbon catalyst;
g) Loading the copper cobalt/carbon catalyst into a catalytic reactor at 10% H 2 /N 2 Reducing for 3h at 250 ℃ in the atmosphere;
h) Selecting methanol and water as raw materials;
i) Methanol and water are mixed in a molar ratio of 1:1.2, fully mixing the components to form a methanol aqueous solution, conveying the methanol aqueous solution into a gasification chamber by using a pressure pump, and converting the methanol aqueous solution into methanol and water vapor under the condition that the temperature is 120 ℃;
j) Introducing a mixed gas of methanol and steam into a reactor filled with a copper-cobalt/carbon catalyst, and generating carbon monoxide and hydrogen at the temperature of 250 ℃;
k) The generated carbon monoxide, hydrogen, unreacted methanol gas and water vapor flow through a condensing device, gaseous methanol and gaseous water are condensed into liquid, and the liquid flows back to a gasification chamber for re-reaction, and the resultant synthetic gas can directly enter other chemical engineering procedures through a separating device.
TABLE 1 Effect of charcoal catalyst on methanol Synthesis gas production
| Gas (es) | Hydrogen gas | Carbon monoxide | Carbon dioxide |
| Content/% | 63.84 | 35.98 | 0.18 |
Example 2:
a) Selecting disposable chopsticks as raw materials, drying the disposable chopsticks at 110 ℃ to remove redundant moisture, and crushing the disposable chopsticks to 5 meshes to form granular and fibrous biomass crushed materials;
b) Placing the biomass crushed material in a nitrogen atmosphere at 600 ℃ for 2h, and removing ash, moisture and organic matters to obtain biomass charcoal particles;
c) Weighing 0.1265g of copper nitrate trihydrate and 0.2270g of cobalt nitrate hexahydrate solid, and adding deionized water to fully dissolve the copper nitrate trihydrate and the cobalt nitrate hexahydrate to form a copper-cobalt mixed solution;
d) Weighing 0.4267g of biochar particles, and placing the biochar particles into a copper-cobalt mixed solution to form a copper-cobalt/carbon mixture;
e) Ultrasonically cleaning a copper-cobalt/carbon mixture at 60 ℃ for 15min, then aging the mixture for 6h at 60 ℃, magnetically stirring the mixture for 20min at 60 ℃, and fully evaporating the water in the mixture at 100 ℃ to obtain a biomass-based catalyst precursor loaded with copper and cobalt elements;
f) Placing the biomass-based catalyst precursor loaded with the copper and cobalt elements in a nitrogen atmosphere with the flow rate of 30ml/min, and roasting for 1.5h at the temperature of 400 ℃ to obtain a copper-cobalt/carbon catalyst;
g) Charging the copper cobalt/carbon catalyst into the catalytic reactor at 20% 2 /N 2 Reducing for 2h at 260 ℃ in the atmosphere;
h) Selecting methanol and water as raw materials;
i) Methanol and water are mixed in a molar ratio of 1:1.5, fully mixing to form a methanol aqueous solution, conveying the methanol aqueous solution into a gasification chamber by using a pressure pump, and converting the methanol aqueous solution into methanol and water vapor under the condition that the temperature is 110 ℃;
j) Introducing a mixed gas of methanol and water vapor into a reactor filled with a copper-cobalt/carbon catalyst, and generating carbon monoxide and hydrogen at the temperature of 270 ℃;
k) The generated carbon monoxide, hydrogen, unreacted methanol gas and water vapor flow through a condensing device, gaseous methanol and gaseous water are condensed into liquid, and the liquid flows back to a gasification chamber for re-reaction, and the resultant synthetic gas can directly enter other chemical engineering procedures through a separating device.
TABLE 2 Effect of charcoal catalyst on methanol synthesis
| Gas (es) | Hydrogen gas | Carbon monoxide | Carbon dioxide |
| Content/% | 61.06 | 38.81 | 0.13 |
The process for preparing synthesis gas from methanol steam and the preparation method of the biomass-based catalyst thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A method for preparing a biomass-based catalyst, comprising:
selecting waste biomass, drying the waste biomass to remove redundant water, and crushing the waste biomass to 5-80 meshes to form granular and fibrous biomass crushed materials;
carbonizing the biomass crushed material in a flowing inert atmosphere, and removing ash, moisture and organic matters to obtain biomass charcoal particles;
preparing a copper-cobalt mixed solution, wherein the molar ratio of copper to cobalt is 1-5;
adding the biomass charcoal particles into the copper-cobalt mixed solution to form a copper-cobalt/charcoal mixture;
ultrasonically cleaning the copper-cobalt/carbon mixture at 40-90 ℃ for 10-20min, then uniformly stirring the mixture at 40-90 ℃ for 20-40min, then aging the mixture at 40-90 ℃ for 6-12h, and then fully evaporating the water in the mixture at 100-120 ℃ to obtain a biomass-based catalyst precursor loaded with copper and cobalt elements;
and placing the biomass-based catalyst precursor loaded with the copper-cobalt element in a flowing nitrogen atmosphere, and roasting to obtain the copper-cobalt/carbon catalyst.
2. The method for preparing a biomass-based catalyst according to claim 1, wherein the temperature of drying is preferably 90-110 ℃ and the degree of crushing is preferably 2-30 mesh in general.
3. The method for preparing the biomass-based catalyst according to claim 1, wherein the inert atmosphere is a nitrogen atmosphere, the carbonization temperature is 450-650 ℃, and the time is 1-2h.
4. The method for producing a biomass-based catalyst according to claim 1, wherein the mass of the biomass charcoal particles is 1 to 10 times the sum of the mass of the copper element and the cobalt element.
5. The method for preparing the biomass-based catalyst according to claim 1, wherein the specific conditions for calcination are as follows: placing in nitrogen atmosphere with flow rate of 20-50ml/min, and calcining at 350-450 deg.C for 1.5-3.5h.
6. A copper cobalt/biochar catalyst prepared by the process of any one of claims 1 to 5.
7. Use of the copper cobalt/biochar catalyst of claim 6 to catalyze methanol steam to syngas.
8. The use of claim 7, comprising:
loading the copper cobalt/biochar catalyst of claim 6 into a catalytic reactor, at 5-50% 2 /N 2 Reducing for 2-4h at 240-260 ℃ in the atmosphere;
methanol and water are mixed in a molar ratio of 1:1-1:5 to form a methanol aqueous solution, sending the methanol aqueous solution into a gasification chamber, and converting the methanol aqueous solution into methanol and water vapor at the temperature of 100-130 ℃;
introducing the mixed gas of methanol and water vapor into a reactor filled with 0.1-0.5g of the copper-cobalt/biochar catalyst, and generating carbon monoxide and hydrogen at the temperature of 220-280 ℃;
the generated carbon monoxide, hydrogen, unreacted methanol gas and water vapor flow through a condensing device, the gaseous methanol and gaseous water are condensed into liquid state and flow back to a gasification chamber for re-reaction, and the resultant synthetic gas can directly enter other chemical engineering procedures through a separating device.
9. The use of claim 8, wherein the condensing means is a water condensing means, and the condensed solution is returned to the vaporizing chamber to participate in the reaction again.
10. The use according to claim 8, wherein the hydrogen and carbon monoxide are produced at a temperature of 15-30 ℃ and at a pressure of atmospheric pressure.
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