CN111377398B - Method for preparing hydrogen and carbon monoxide by biomass pyrolysis and gasification - Google Patents
Method for preparing hydrogen and carbon monoxide by biomass pyrolysis and gasification Download PDFInfo
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- CN111377398B CN111377398B CN201811618218.8A CN201811618218A CN111377398B CN 111377398 B CN111377398 B CN 111377398B CN 201811618218 A CN201811618218 A CN 201811618218A CN 111377398 B CN111377398 B CN 111377398B
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- 239000002028 Biomass Substances 0.000 title claims abstract description 87
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 62
- 239000001257 hydrogen Substances 0.000 title claims abstract description 62
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 62
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002309 gasification Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 38
- OXLRDKBGARCSLL-UHFFFAOYSA-N [Ca].[Co]=O Chemical group [Ca].[Co]=O OXLRDKBGARCSLL-UHFFFAOYSA-N 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 239000001569 carbon dioxide Substances 0.000 claims description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 239000002154 agricultural waste Substances 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- -1 perovskite Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000006479 redox reaction Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000011286 gas tar Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007353 oxidative pyrolysis Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing hydrogen and carbon monoxide by pyrolyzing and gasifying biomass, which comprises the following steps: (1) the biomass raw material, the oxygen carrier and the catalyst enter a biomass pyrolysis gasification reactor and contact with steam to carry out pyrolysis gasification reaction; (2) and (3) the solid phase material obtained in the step (2) enters a carbon monoxide preparation reactor for reaction, and the material obtained after the reaction is subjected to gas-solid separation to obtain carbon monoxide, a regenerated catalyst and an oxygen carrier. In the method, the high-efficiency gasification of biomass is realized to prepare hydrogen and carbon monoxide by the circulating catalytic oxidation reduction of the catalyst and the oxygen carrier.
Description
Technical Field
The invention belongs to the technical field of biomass utilization, relates to a biomass pyrolysis gasification treatment method, and particularly relates to a method for preparing hydrogen and carbon monoxide by biomass gasification.
Background
The global energy supply mainly takes fossil energy as main energy, and the rapid development of the economic society is strongly supported. However, fossil energy is a non-renewable resource, and development of renewable energy is imperative in order to adapt to future economic development. Biomass is an organism formed by direct or indirect photosynthesis, has the characteristics of wide distribution, large available amount and the like, and is very important renewable energy. The biomass conversion and utilization ways are numerous, wherein the biomass thermochemical conversion raw material has wide variety adaptability, is easy to popularize and apply in large scale, and receives more and more attention.
The main products of biomass pyrolysis gasification are low-carbon hydrocarbon mixed gas such as hydrogen, carbon monoxide, carbon dioxide and methane, and the current main process product routes are divided into three routes: firstly, the above-mentioned mixed combustible gas of biomass gasification system, the combustible gas tar content that the living beings were prepared is higher, and compares in civil gas, and the calorific value is on the low side, is difficult to the use of being incorporated into the power networks. Secondly, the synthesis gas rich in hydrogen and carbon monoxide is prepared by process optimization, the synthesis gas is an important chemical raw material gas, various high-added-value products can be further synthesized, but the synthesis gas prepared from biomass is low in hydrogen/carbon monoxide ratio and difficult to regulate and control, cannot reach the synthesis gas standard in the real sense, and is not beneficial to subsequent direct utilization. Patent CN103484163A discloses a method for preparing pure synthesis gas by biomass dual-mode reforming gasification, which comprises the steps of performing partial oxidation pyrolysis on biomass and oxygen, performing reforming reaction on pyrolysis products and steam under the action of a nickel-based catalyst to generate synthesis gas, wherein the synthesis gas comprises hydrogen, carbon monoxide, methane and carbon dioxide. And thirdly, hydrogen-rich gas is obtained through process optimization, the hydrogen is clean, efficient and environment-friendly ideal energy, but the hydrogen production from the biomass wastes a carbon source in the biomass, the carbon source is changed into greenhouse gas carbon dioxide, and the efficient utilization of biomass resources is not realized. Patent CN104129754A discloses a biomass pyrolysis and chemical looping hydrogen production coupling continuous reaction device and a method for preparing hydrogen by using the device, biomass is firstly pyrolyzed to generate pyrolysis gas, the reduction property of the biomass pyrolysis gas is utilized to perform redox reaction with an oxygen carrier film, the oxygen carrier is reduced, finally the reduced oxygen carrier reacts with water vapor to generate hydrogen, and the oxygen carrier film is recovered.
Therefore, how to fully utilize biomass resources and improve the quality of biomass gasification product gas is a problem to be further solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing hydrogen and carbon monoxide by biomass pyrolysis and gasification, wherein the method realizes the efficient gasification of biomass to prepare hydrogen and carbon monoxide by the circulating catalytic oxidation reduction of a catalyst and an oxygen carrier.
The invention provides a method for preparing hydrogen and carbon monoxide by pyrolyzing and gasifying biomass, which comprises the following steps:
(1) the biomass raw material, the oxygen carrier and the catalyst enter a biomass pyrolysis gasification reactor and contact with steam to carry out pyrolysis gasification reaction;
(2) the reaction effluent in the step (1) is subjected to gas-solid separation to obtain hydrogen and solid-phase materials,
(3) and (3) allowing the solid-phase material obtained in the step (2) to enter a carbon monoxide preparation reactor for reaction, and performing gas-solid separation on the material obtained after the reaction to obtain carbon monoxide, a regenerated catalyst and an oxygen carrier.
In the method for preparing hydrogen and carbon monoxide by pyrolyzing and gasifying biomass, the biomass raw material in the step (1) is agricultural waste such as straw and the like, forestry waste such as sawdust and the like or a mixture of the agricultural waste and the forestry waste, the biomass raw material is preferably dried or baked in the air before being used, and is crushed, and the particle size of the crushed biomass raw material is 0.5-30 mm.
In the method for preparing hydrogen and carbon monoxide by biomass pyrolysis gasification, the pyrolysis gasification reaction temperature in the step (1) is 800-1200 ℃, and preferably 800-1000 ℃.
In the method for preparing hydrogen and carbon monoxide by biomass pyrolysis and gasification, the mass ratio of the steam introduced in the pyrolysis and gasification reaction in the step (1) to the biomass raw material is 0.1-5: 1.
In the method for preparing hydrogen and carbon monoxide by pyrolyzing and gasifying biomass, the mass ratio of the biomass raw material, the catalyst and the oxygen carrier in the step (1) is 0.1-3: 0.1-3, and preferably 0.1-2: 0.1-2.
In the method for preparing hydrogen and carbon monoxide by biomass pyrolysis gasification, the catalyst in the step (1) is a calcium-cobalt oxide catalyst, specifically can be one or more of a calcium-cobalt oxide monomer and a supported calcium-cobalt oxide catalyst, and a carrier of the supported calcium-cobalt oxide catalyst can be one or more of alumina, perovskite, titanium dioxide and spinel. The calcium cobalt oxide is composed of calcium oxide and cobalt oxide, wherein the mass ratio of the calcium oxide to the cobalt oxide is 0.1: 1-4: 1, and preferably 1: 1-3: 1.
In the method for preparing hydrogen and carbon monoxide by biomass pyrolysis gasification, in the step (1), the oxygen carrier is an iron-based oxygen carrier, the iron-based oxygen carrier can be one or more of iron oxide and supported iron oxide, the supported iron oxide comprises an active component and a carrier, the active component is the iron oxide, the carrier can be one or more of perovskite compound, spinel, titanium dioxide or aluminum oxide, and the mass ratio of the active component to the carrier is 0.1: 1-5: 1, preferably 0.5: 1-2: 1.
In the method for preparing hydrogen and carbon monoxide by pyrolysis and gasification of biomass, the reaction temperature in the step (3) is 700-1000 ℃, and preferably 750-900 ℃.
In the method for preparing hydrogen and carbon monoxide by biomass pyrolysis gasification, a biomass pyrolysis gasification reactor in the step (1) is a moving bed reactor, and is preferably a descending moving bed reactor, a biomass raw material, a catalyst and an oxygen carrier are added from the top of the reactor, water vapor is introduced from the upper end of the reactor, gas-solid two-phase materials flow from top to bottom together, the catalyst and the oxygen carrier play double roles to catalyze and promote the biomass pyrolysis gasification at 800-1200 ℃, hydrogen and carbon dioxide are mainly generated, the carbon dioxide is absorbed by calcium oxide to generate calcium carbonate for fixation, the hydrogen is led out of the reactor for collection, and a catalyst containing calcium carbonate and a reduced oxygen carrier enter a reactor for preparing carbon monoxide together.
In the method for preparing hydrogen and carbon monoxide by biomass pyrolysis gasification, the reactor for preparing carbon monoxide in the step (3) is a moving bed reactor, and is preferably a downward moving bed reactor, solid-phase materials separated from the reactor for biomass pyrolysis gasification are added from the top end of the reactor for preparing carbon monoxide, move from top to bottom and react, at 700-1000 ℃, the catalyst containing calcium carbonate separated in the step (1) is thermally decomposed to generate oxide catalyst and carbon dioxide, the regeneration of the catalyst is completed, the carbon dioxide generated by thermal decomposition further performs redox reaction with a reduced oxygen carrier to generate oxygen carrier and carbon monoxide, the regeneration of the oxygen carrier and the co-production of carbon monoxide are realized, finally, the carbon monoxide is led out and collected, and the catalyst and the oxygen carrier are recycled.
Compared with the prior art, the method for preparing hydrogen and carbon monoxide by pyrolyzing and gasifying biomass has the following advantages.
1. The invention realizes the respective preparation of hydrogen and carbon monoxide by the pyrolysis and gasification of biomass, solves the problems of complex components and difficult utilization of the existing biomass pyrolysis gas, and improves the value of product gas. The prepared hydrogen and carbon monoxide can be mixed in a proper proportion to be used as synthesis gas for Fischer-Tropsch synthesis, and can also be used independently, for example, the hydrogen can be used for hydrogen fuel cells, petroleum industry oil refining hydrogenation and the like, and the carbon monoxide can be used in the aspects of metallurgical industry, household fuel gas and the like, so that high-value utilization of products is realized.
2. According to the method for preparing hydrogen and carbon monoxide by biomass pyrolysis gasification, biomass raw materials are subjected to pyrolysis gasification reaction in a biomass pyrolysis reactor under the catalytic action of calcium-cobalt oxide and the promotion of oxidative pyrolysis of an iron-based oxygen carrier, gas products obtained by the reaction mainly comprise hydrogen and carbon dioxide, wherein the carbon dioxide can act with the calcium-cobalt oxide catalyst and generate carbonate to be fixed on the calcium-cobalt oxide catalyst, so that the separation of the hydrogen and the carbon dioxide is easily realized, and the high-purity hydrogen is obtained.
3. In the method for preparing hydrogen and carbon monoxide by biomass pyrolysis gasification, in a carbon monoxide preparation reactor, a catalyst absorbing carbon dioxide is heated and decomposed to regenerate a calcium cobalt oxide carrier and carbon dioxide, and the decomposed carbon dioxide can further carry out redox reaction with a reduced iron-based oxygen carrier to generate carbon monoxide.
4. The method for preparing hydrogen and carbon monoxide by biomass pyrolysis gasification realizes the preparation of high-purity hydrogen and carbon monoxide by catalyst catalysis and chemical chain oxidation-reduction reaction of an oxygen carrier, and simultaneously completes the regeneration of the catalyst and the oxygen carrier in the reaction process without additional treatment, thereby greatly reducing the energy consumption of the whole method and optimizing the reaction route.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The biomass raw materials in the embodiment and the comparative example of the invention are naturally air-dried corn straws which are crushed to the granularity of 1-5 mm.
The invention provides a method for preparing hydrogen and carbon monoxide by pyrolyzing and gasifying biomass, which comprises the following steps: the biomass raw material, the oxygen carrier and the catalyst enter a biomass pyrolysis gasification reactor and contact with steam to carry out pyrolysis gasification reaction; the method comprises the steps of carrying out pyrolysis gasification reaction at 800-1200 ℃ under the dual catalytic promotion of a calcium-cobalt oxide catalyst and an iron-based oxygen carrier, wherein a gas-phase product mainly comprises hydrogen and carbon dioxide, the carbon dioxide is absorbed and fixed by the calcium-cobalt oxide catalyst to generate a calcium carbonate-containing catalyst, the iron-based oxygen carrier and biomass are subjected to partial oxidation pyrolysis reaction and then are converted into a reduced-state oxygen carrier, a pyrolysis product is separated by a cyclone separator, the hydrogen is taken as a product to be led out and collected, the solid calcium carbonate-containing catalyst and the reduced-state oxygen carrier enter a carbon monoxide preparation reactor, the calcium carbonate-containing catalyst is heated and decomposed at 700-1000 ℃ to release the carbon dioxide, the calcium-cobalt oxide catalyst is regenerated, the carbon dioxide and the reduced-state oxygen carrier are subjected to oxidation reduction reaction to generate carbon monoxide, the regeneration of the iron-based oxygen carrier is realized at the same time, and the reaction product is subjected to cyclone separation, and carbon monoxide is led out and collected from an outlet, and the regenerated calcium-cobalt oxide catalyst and the iron-based oxygen carrier are recycled and flow into the biomass pyrolysis gasification reactor for circular reaction.
Example 1
Preparation of calcium cobalt oxide catalyst: calcium nitrate Ca (NO)3)2And cobalt nitrate Co (NO)3)2·6H2Dissolving O in deionized water according to the mass ratio of 0.56:1, quickly stirring for 4 hours, and drying the mixed solution for 24 hours at 120 ℃; and calcining the obtained catalyst precursor for 4 hours at 1000 ℃ in an air atmosphere, and forming and screening to obtain the catalyst with the granularity of 30-40 meshes.
Example 2
The method of the invention adopts a calcium cobalt oxide catalyst and an iron-based oxide oxygen carrier, the specific reaction conditions are shown in table 1, and the reaction results are shown in table 2.
Example 3
The method adopts the calcium-cobalt oxide catalyst and the load type iron-based oxygen carrier, the specific reaction conditions are shown in table 1, and the reaction results are shown in table 2.
Comparative example 1
Compared with the example 2, only the calcium cobalt oxide catalyst and no oxygen carrier exist, the specific reaction conditions are shown in the table 1, and the reaction results are shown in the table 2.
TABLE 1 reaction conditions
TABLE 2 results of the reaction
The above-mentioned embodiments are merely preferred embodiments of the present invention, and the present invention is not limited thereto, and those skilled in the art can easily practice the present invention according to the above-mentioned embodiments, and any changes, modifications, improvements, equivalent replacements, etc. within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (15)
1. A method for preparing hydrogen and carbon monoxide by biomass pyrolysis gasification, which comprises the following steps:
(1) the biomass raw material, the oxygen carrier and the catalyst enter a biomass pyrolysis gasification reactor and contact with steam to carry out pyrolysis gasification reaction, the catalyst is a calcium cobalt oxide catalyst, the calcium cobalt oxide catalyst is composed of calcium oxide and cobalt oxide, and the calcium cobalt oxide catalyst is composed of calcium nitrate Ca (NO)3)2And cobalt nitrate Co (NO)3)2·6H2Dissolving O according to the mass ratio of 0.56:1, drying and calcining to obtain the catalystThe biomass pyrolysis gasification is promoted under the dual action of the oxygen carrier, hydrogen and carbon dioxide are mainly generated, and the carbon dioxide is absorbed by calcium oxide to generate calcium carbonate for fixation;
(2) carrying out gas-solid separation on the reaction effluent in the step (1) to obtain hydrogen and a solid-phase material;
(3) and (3) allowing the solid-phase material obtained in the step (2) to enter a carbon monoxide preparation reactor for reaction, and performing gas-solid separation on the material obtained after the reaction to obtain carbon monoxide, a regenerated catalyst and an oxygen carrier.
2. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 1 wherein: the biomass raw material in the step (1) is agricultural waste, forestry waste or a mixture thereof.
3. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 1 wherein: and (2) naturally drying or baking the biomass raw material in the step (1) before use, and crushing the biomass raw material, wherein the granularity of the crushed biomass raw material is 0.5-30 mm.
4. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 1 wherein: in the step (1), the pyrolysis gasification reaction temperature is 800-1200 ℃.
5. The process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 4 wherein: in the step (1), the pyrolysis gasification reaction temperature is 800-1000 ℃.
6. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 1 wherein: the mass ratio of the steam introduced into the pyrolysis gasification reaction in the step (1) to the biomass raw material is 0.1-5: 1.
7. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 1 wherein: the mass ratio of the biomass raw material, the catalyst and the oxygen carrier in the step (1) is 0.1-3: 0.1-3.
8. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 1 wherein: the mass ratio of the biomass raw material, the catalyst and the oxygen carrier in the step (1) is 0.1-2: 0.1-2.
9. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 1 wherein: in the step (1), the calcium cobalt oxide catalyst is one or more of a calcium cobalt oxide monomer and a supported calcium cobalt oxide catalyst, and a carrier of the supported calcium cobalt oxide catalyst is one or more of alumina, perovskite, titanium dioxide and spinel.
10. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 1 wherein: the oxygen carrier in the step (1) is an iron-based oxygen carrier.
11. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 10 wherein: the iron-based oxygen carrier is one or more of iron oxide and supported iron oxide.
12. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 11 wherein: the load type iron oxide comprises an active component and a carrier, wherein the active component is iron oxide, the carrier is one or more of a perovskite type compound, spinel, titanium dioxide or aluminum oxide, and the mass ratio of the active component to the carrier is 0.1: 1-5: 1.
13. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 12 wherein: the mass ratio of the active component to the carrier is 0.5: 1-2: 1.
14. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 11 wherein: in the step (3), the reaction temperature is 700-1000 ℃.
15. A process for producing hydrogen and carbon monoxide by pyrolysis gasification of biomass as claimed in claim 11 wherein: in the step (3), the reaction temperature is 750-900 ℃.
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| CN101570315B (en) * | 2009-06-15 | 2011-06-01 | 江苏大学 | Method and device for producing hydrogen through biomass gasification by using single fluidized bed and two-step method |
| EP2539273A1 (en) * | 2010-02-23 | 2013-01-02 | Total SA | Method for producing synthesis gases |
| CN105358475A (en) * | 2013-02-05 | 2016-02-24 | 俄亥俄州国家创新基金会 | Methods for fuel conversion |
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| EP1281747A2 (en) * | 2001-07-31 | 2003-02-05 | General Electric Company | A process for converting coal into fuel cell quality hydrogen |
| CN101570315B (en) * | 2009-06-15 | 2011-06-01 | 江苏大学 | Method and device for producing hydrogen through biomass gasification by using single fluidized bed and two-step method |
| EP2539273A1 (en) * | 2010-02-23 | 2013-01-02 | Total SA | Method for producing synthesis gases |
| CN105358475A (en) * | 2013-02-05 | 2016-02-24 | 俄亥俄州国家创新基金会 | Methods for fuel conversion |
| CN105858601A (en) * | 2016-04-07 | 2016-08-17 | 中国石油化工股份有限公司 | Switchover-type chemical-looping hydrogen production plant and hydrogen production method |
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Effective date of registration: 20231013 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |