CN114433139A - Biological coke gasification catalyst and biological coke catalytic raw material - Google Patents
Biological coke gasification catalyst and biological coke catalytic raw material Download PDFInfo
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- CN114433139A CN114433139A CN202011193773.8A CN202011193773A CN114433139A CN 114433139 A CN114433139 A CN 114433139A CN 202011193773 A CN202011193773 A CN 202011193773A CN 114433139 A CN114433139 A CN 114433139A
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- China
- Prior art keywords
- biocoke
- raw material
- carbonate
- bromide
- iodide
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- 239000000571 coke Substances 0.000 title claims abstract description 114
- 238000002309 gasification Methods 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 40
- 239000002994 raw material Substances 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 37
- 150000008045 alkali metal halides Chemical class 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 26
- -1 alkaline earth metal carbonate Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 25
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 24
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 21
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 16
- 239000001103 potassium chloride Substances 0.000 claims description 15
- 235000011164 potassium chloride Nutrition 0.000 claims description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 239000001095 magnesium carbonate Substances 0.000 claims description 10
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 9
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 8
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 8
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 8
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- JAAGVIUFBAHDMA-UHFFFAOYSA-M rubidium bromide Chemical compound [Br-].[Rb+] JAAGVIUFBAHDMA-UHFFFAOYSA-M 0.000 claims description 8
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 8
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 8
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 235000009518 sodium iodide Nutrition 0.000 claims description 8
- 239000002028 Biomass Substances 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- HOTRSNBZKAJMEW-UHFFFAOYSA-M [Br-].[Fr+] Chemical compound [Br-].[Fr+] HOTRSNBZKAJMEW-UHFFFAOYSA-M 0.000 claims description 4
- REHSTLKSMMQUJZ-UHFFFAOYSA-M [F-].[Fr+] Chemical compound [F-].[Fr+] REHSTLKSMMQUJZ-UHFFFAOYSA-M 0.000 claims description 4
- BGVAXUQNVLJVFE-UHFFFAOYSA-M [I-].[Fr+] Chemical compound [I-].[Fr+] BGVAXUQNVLJVFE-UHFFFAOYSA-M 0.000 claims description 4
- YPWICUOZSQYGTD-UHFFFAOYSA-L [Ra+2].[O-]C([O-])=O Chemical compound [Ra+2].[O-]C([O-])=O YPWICUOZSQYGTD-UHFFFAOYSA-L 0.000 claims description 4
- ZBUQRSWEONVBES-UHFFFAOYSA-L beryllium carbonate Chemical compound [Be+2].[O-]C([O-])=O ZBUQRSWEONVBES-UHFFFAOYSA-L 0.000 claims description 4
- 229910000023 beryllium carbonate Inorganic materials 0.000 claims description 4
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 4
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000011698 potassium fluoride Substances 0.000 claims description 4
- 235000003270 potassium fluoride Nutrition 0.000 claims description 4
- 229940102127 rubidium chloride Drugs 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- ROZPZBUZWPOKFI-UHFFFAOYSA-M [Cl-].[Fr+] Chemical compound [Cl-].[Fr+] ROZPZBUZWPOKFI-UHFFFAOYSA-M 0.000 claims description 3
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 210000003608 fece Anatomy 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000010871 livestock manure Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 239000007789 gas Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 12
- 230000004907 flux Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 240000009226 Corylus americana Species 0.000 description 1
- 235000001543 Corylus americana Nutrition 0.000 description 1
- 235000007466 Corylus avellana Nutrition 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
-
- 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
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
-
- 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
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
-
- 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
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a biological coke gasification catalyst and a biological coke catalytic raw material. The biocoke catalytic feedstock includes a biocoke feedstock, an alkali metal halide, and an alkaline earth metal carbonate. The biological coke catalytic raw material can be prepared by adopting a dry method or a wet method. When the gasification catalyst is used for the steam gasification reaction of the biological coke, the water conversion rate and the yield of the synthetic gas can be greatly improved, and the gasification reaction activity of the biological coke is obviously improved.
Description
Technical Field
The invention relates to the field of biological coke gasification, in particular to a biological coke gasification catalyst and a biological coke catalytic raw material.
Background
The biomass pyrolysis technology can convert biomass into high-added-value products such as fuel gas, synthesis gas, bio-oil and the like, realizes high-efficiency conversion and utilization of biomass energy, and the biomass semi-coke serving as a pyrolysis solid product has the content of about 10-30% of the pyrolysis gasification product and has extremely rich recycling energy. The biological coke has a complex pore structure and good surface chemical characteristics, and can effectively adsorb and remove components such as heavy metals, polycyclic aromatic hydrocarbons and the like in soil, water and flue gas, so that most of the further utilization of the biological coke is concentrated on the application aspects such as soil conditioners, adsorbents and the like. The method actively explores the biological coke gasification technology, adopts low-quality biological coke to produce high-quality synthetic gas products with wide application, realizes high-value utilization of the biological coke, and has important significance on the integrity and the economy of the biomass pyrolysis process.
The common gasification agents for coke gasification reaction are carbon dioxide and steam, and under the same reaction conditions, the gasification reaction rate of the coke and the steam is obviously higher than that of the carbon dioxide, so that the steam gasification reaction of the biological coke is one of effective ways for rapid high-value utilization. Under the non-catalytic gasification condition, the reaction activity of the steam gasification reaction of the biological coke is low, and the steam gasification activity of the biological coke can be obviously improved by adding the gasification catalyst. The catalysts for biological coke gasification mainly comprise oxides and salts of alkali metals, alkaline earth metals and transition metals, wherein potassium salts are the best catalytic activity. The potassium carbonate in the potassium salt has the most obvious catalytic effect, but the expensive price of the potassium carbonate becomes the main problem that the cost for catalyzing and gasifying the biological coke is high, and the large-scale use also becomes a difficult problem. How to improve the cheap gasification catalytic raw materials becomes a key problem for accelerating the deep utilization of the biological coke gasification technology.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a biological coke gasification catalyst and application thereof, wherein a catalytic material with low price and wide source is used as the biological coke gasification catalyst to improve the activity of the biological coke gasification reaction.
In a first aspect, the invention provides a biocoke gasification catalyst comprising an alkali metal halide and an alkaline earth metal carbonate.
In the above biological coke gasification catalyst, the mass ratio of the alkali metal halide to the alkaline earth metal carbonate is 30: 1-1: 5, preferably 6: 1-1: 1.
in the above-mentioned biocoke gasification catalyst, the alkali metal halide may be specifically selected from one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride francium, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, francium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, and francium iodide, and is preferably one or more of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, and potassium iodide.
In the biological coke gasification catalyst, the alkaline earth metal carbonate is one or more of beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and radium carbonate, and preferably one or more of magnesium carbonate and calcium carbonate.
In a second aspect, the invention provides a biocoke catalytic feedstock comprising a biocoke feedstock, an alkali metal halide, and an alkaline earth metal carbonate.
Further, the biological coke raw material can be a solid product obtained by performing processes such as pyrolysis or and liquefaction or carbonization on biomass such as agricultural residues, forestry wastes, household garbage, waste plastics, animal wastes and the like.
Further, the particle size of the raw material of the biological coke is less than 2 mm.
Further, the alkali metal halide may be specifically selected from one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, francium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, francium iodide, and preferably one or more of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, and potassium iodide.
Further, the alkaline earth metal carbonate is one or more of beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and radium carbonate, and preferably one or more of magnesium carbonate and calcium carbonate.
Further, in the biological coke catalytic raw material, the mass ratio of the sum of the alkali metal halide and the alkaline earth metal carbonate to the biological coke raw material is 50-4: 96-50, wherein the mass ratio of the alkali metal halide to the alkaline earth metal carbonate is 30: 1-1: 5, preferably 6: 1-1: 1.
the third aspect of the invention provides a preparation method of a biological coke catalytic raw material, which comprises the steps of mixing the biological coke raw material, alkali metal halide and alkaline earth metal carbonate, uniformly mixing, and drying to obtain the biological coke catalytic raw material.
Further, in the preparation method, the drying temperature is 60-120 ℃.
Furthermore, in the above preparation method, the mixing may be any means capable of achieving uniform mixing of solid phase materials in the prior art, such as grinding and stirring.
In a fourth aspect, the present invention provides a method for preparing a biocoke catalytic raw material according to another embodiment, the method comprising the following steps:
(1) mixing alkali metal halide with water to prepare an alkali metal halide aqueous solution;
(2) mixing a biological coke raw material with the alkali metal halide aqueous solution obtained in the step (1), uniformly mixing, and drying to obtain the biological coke loaded with the alkali metal halide;
(3) and (3) mixing the biological coke loaded with the alkali metal halide obtained in the step (2) with the alkaline earth metal carbonate, uniformly mixing, and drying to obtain the biological coke catalytic raw material.
Further, in the preparation method, the addition amount of the water is the saturated water absorption amount of the equivalent ratio of the biological coke, and the addition amount of the water is 1.5-2 g of water/g of biological coke according to the type of the biological coke and the air humidity.
Further, in the preparation method, the drying temperature in the step (2) is 60-120 ℃.
Further, in the preparation method, the drying temperature in the step (3) is 100-120 ℃.
Furthermore, in the above preparation method, the mixing may be any means capable of achieving uniform mixing of solid phase materials in the prior art, such as grinding and stirring.
The fifth aspect of the invention provides a biological coke gasification process, wherein the prepared biological coke catalytic raw material is contacted with steam in a gasification furnace to generate gasification reaction.
In the biological coke gasification process, the gasification reaction temperature is 700-950 ℃.
In the biological coke gasification process, the mass ratio of the water vapor to the biological coke raw material in the biological coke gasification reaction process is 0.1-10, preferably 0.2-8.
Compared with the prior art, the biological coke gasification catalyst and the biological coke catalytic raw material provided by the invention have the following technical effects:
1. the biological coke gasification catalyst provided by the invention comprises alkali metal halide and alkaline earth metal carbonate, when the catalyst is used in the biological coke steam gasification process, the alkali metal halide and the alkaline earth metal carbonate generate alkali metal carbonate in situ through ion exchange reaction, and the alkali metal carbonate generated in situ is a metastable compound, and the activity of the metastable compound is higher than that of the alkali metal carbonate directly added. When the catalyst is used for the steam gasification reaction of the biological coke, the water conversion rate and the yield of the synthesis gas can be greatly improved, the gasification reaction activity of the biological coke is obviously improved, the source of the alkali metal halide serving as the raw material of the catalyst is wide, the alkali metal halide can be obtained from natural ore and seawater, the price is low, the cost of the biological coke gasification catalyst is greatly reduced, and the problem of low catalytic activity when the alkali metal halide is singly used as a catalytic component is solved.
2. The biological coke gasification catalyst provided by the invention can form a series of low-melting-point eutectic mixtures by alkali metal halides and alkaline earth metal carbonates under reaction conditions, the melting point of the eutectic is far lower than that of a single component, the eutectic is not solid any more at the reaction temperature, but exists in a liquid state in a reaction system, the contact area between the biological coke and the gasification catalyst is greatly increased, the mobility of alkali metal is enhanced, and thus the gasification reaction activity of the biological coke is greatly improved. More importantly, the low-melting-point eutectic mixture of the alkali metal halide and the alkaline earth metal halide has a remarkable promoting effect on the gasification reaction activity of the biological coke, and also plays a good role in the aspect of fixing the alkali metal, thereby greatly reducing the volatilization amount of the alkali metal.
3. The biological coke gasification catalyst provided by the invention improves the gasification reaction activity of the biological coke, converts low-value biological coke into a high-calorific-value synthesis gas product, realizes high-value utilization of the biological coke, and widens the utilization path of the biological coke.
4. The biological coke gasification catalyst used in the invention can effectively reduce the temperature required by biological coke gasification, and the composite catalyst system used in the invention has ion exchange effect and low-melting-point eutectic effect under reaction conditions, so that the catalytic effect is far stronger than that of a single catalyst, and the time required by gasification is shortened.
Detailed Description
The present invention will be described in more detail with reference to examples and comparative examples, but the scope of the present invention is not limited by the examples.
Example 1
Weighing 1.1g of KCl, adding the KCl into 20g of water, fully and uniformly mixing to obtain a KCl aqueous solution, weighing 14g of rice hull pyrolytic biological coke with the particle size of less than 2mm, mixing with the KCl aqueous solution, and treating for 6 hours under stirring; then the uniformly mixed materials are put into a blast drying oven to be dried for 6 hours at the temperature of 80 ℃ to obtain the impregnated KBiological coke of Cl, mixing the above sample with 0.91g CaCO3Uniformly mixing, then drying in a forced air drying oven at 120 ℃ for 4 hours, and then putting the obtained sample into a microwave fixed bed reactor to carry out steam gasification reaction under the following reaction conditions: the temperature is 850 ℃, the pressure is normal, the flux of water is 0.5mL/min, after 50min of reaction, the average water conversion rate in the reaction process is 84%, and the yield of the synthetic gas is 1068g/kg biological coke.
Example 2
Weighing 16g of rice hull pyrolytic biological coke with particle size less than 2mm, 0.7g of KCl and 0.43g of CaCO3Uniformly mixing the samples, then drying the samples in a blast drying oven at 105 ℃ for 5 hours to obtain biological coke loaded with a catalyst, putting the samples on a microwave fixed bed reactor to carry out steam gasification reaction, wherein the reaction conditions are as follows: the temperature is 800 ℃, the pressure is normal, the flux of water is 0.6mL/min, after 40min of reaction, the average water conversion rate in the reaction process is 75%, and the yield of the synthetic gas is 893g/kg of biological coke.
Example 3
Weighing 13g of rice hull pyrolytic biological coke with particle size less than 2mm, 1.5g of NaCl and 0.6g of CaCO3Uniformly mixing the samples, then placing the samples into a blast drying oven to be dried for 5 hours at the temperature of 110 ℃ to obtain biological coke loaded with a catalyst, placing the samples into a microwave fixed bed reactor to carry out steam gasification reaction, wherein the reaction conditions are as follows: the temperature is 850 ℃, the pressure is normal, the flux of water is 0.35mL/min, after 65min of reaction, the average water conversion rate in the reaction process is 85%, and the yield of the synthetic gas is 1140g/kg of biological coke.
Example 4
Weighing 12g of plastic pyrolytic biological coke with the particle size less than 2mm, 1.6g of NaBr and 0.2g of CaCO3、0.8gMgCO3Uniformly mixing the samples, then drying the samples in a blast drying oven at 105 ℃ for 7 hours to obtain biological coke loaded with a catalyst, putting the samples in a microwave fixed bed reactor to carry out steam gasification reaction, wherein the reaction conditions are as follows: the temperature is 750 ℃, the pressure is normal, the flux of water is 0.3mL/min, after 75min of reaction, the average water conversion rate in the reaction process is 71%, and the yield of the synthetic gas is 1203g/kg biological coke.
Example 5
Weighing 13g of plastic pyrolytic biological coke with the particle size of less than 2mm, 1.4gKF g and 2.1g of MgCO3Uniformly mixing the samples, then placing the samples into a blast drying oven to be dried for 12 hours at the temperature of 100 ℃ to obtain biological coke loaded with a catalyst, and placing the samples into a microwave fixed bed reactor to carry out steam gasification reaction under the following reaction conditions: the temperature is 900 ℃, the pressure is normal, the flux of water is 0.5mL/min, after 75min of reaction, the average water conversion rate in the reaction process is 45%, and the yield of the synthetic gas is 821g/kg biological coke.
Example 6
Weighing 30g of pine carbonized biocoke with particle size less than 2mm, 1g of KCl and 0.16g of CaCO3Uniformly mixing the samples, then placing the samples into a blast drying oven to be dried for 12 hours at the temperature of 100 ℃ to obtain biological coke loaded with a catalyst, placing the samples onto a microwave fixed bed reactor to carry out steam gasification reaction, wherein the reaction conditions are as follows: the temperature is 750 ℃, the pressure is normal, the flux of water is 0.3mL/min, after 50min of reaction, the average water conversion rate in the reaction process is 48%, and the yield of the synthetic gas is 301g/kg biological coke.
Example 7
Weighing 16g of hazelnut carbonized biological coke with the grain diameter less than 2mm, 8g of NaBr and 0.89g of MgCO3Uniformly mixing the samples, then placing the samples into a blast drying oven to be dried for 12 hours at the temperature of 100 ℃ to obtain biological coke loaded with a catalyst, and placing the samples into a microwave fixed bed reactor to carry out steam gasification reaction under the following reaction conditions: the temperature is 950 ℃, the pressure is normal, the flux of water is 0.3mL/min, after 45min of reaction, the average water conversion rate in the reaction process is 88 percent, and the yield of the synthetic gas is 986g/kg of biological coke.
Comparative example 1
Weighing 15g of cow dung pyrolytic biological coke with the particle size smaller than 2mm, and carrying out steam gasification on a microwave fixed bed reactor, wherein the reaction conditions are as follows: the temperature is 700 ℃, the pressure is normal, the flux of water is 0.2mL/min, the average water conversion rate in the reaction process of reacting for 70min is 9 percent, and the yield of the synthetic gas is 52g/kg biological coke.
Comparative example 2
Weighing 15g of spruce gasified biological coke with the particle size less than 2mm, and carrying out steam gasification on a microwave fixed bed reactor, wherein the reaction conditions are as follows: the temperature is 1100 ℃, the pressure is normal, the flux of water is 0.3mL/min, the average water conversion rate in the reaction process of reacting for 70min is 90 percent, and the yield of the synthetic gas is 1272g/kg biological coke.
Comparative example 3
Weighing 16g of rice hull pyrolysis biological coke with the particle size of less than 2mm and 0.7g of KCl, uniformly mixing the samples, then drying the samples in a blast drying oven at 105 ℃ for 5 hours to obtain catalyst-loaded biological coke, putting the samples on a microwave fixed bed reactor for steam gasification reaction, wherein the reaction conditions are as follows: the temperature is 800 ℃, the pressure is normal, the flux of water is 0.6mL/min, after 40min of reaction, the average water conversion rate in the reaction process is 58%, and the yield of the synthetic gas is 514g/kg biological coke.
Comparative example 4
Weighing 13g of rice hull pyrolytic biological coke with particle size less than 2mm and 0.6g of CaCO3Uniformly mixing the samples, then placing the samples into a blast drying oven to be dried for 5 hours at the temperature of 110 ℃ to obtain biological coke loaded with a catalyst, placing the samples into a microwave fixed bed reactor to carry out steam gasification reaction, wherein the reaction conditions are as follows: the temperature is 850 ℃, the pressure is normal, the flux of water is 0.35mL/min, after 65min of reaction, the average water conversion rate in the reaction process is 42%, and the yield of the synthetic gas is 435g/kg of biological coke.
From the data analysis of comparative examples 1 to 4 and examples 1 to 7, it is understood that when an alkali metal halide is added alone as a catalyst during steam gasification of biocoke, the gasification activity of the biocoke is slightly improved, and when an alkaline earth metal carbonate is added alone, the gasification activity of the biocoke is rather lowered. The alkali metal halide and the alkaline earth metal carbonate are added simultaneously to generate a metastable active component through an ion exchange reaction in a steam atmosphere, so that the catalytic gasification activity of the biological coke is far higher than that of the biological coke added with the alkali metal halide or the alkaline earth metal carbonate alone, the steam gasification of the biological coke can be carried out at a lower temperature, the average water conversion rate and the synthesis gas yield are greatly improved, and the gasification reaction activity of the biological coke is remarkably improved. In addition, compared with the traditional expensive potassium carbonate catalyst, the two catalytic raw materials have low price and wide sources, can be used as a disposable catalyst and not be recycled, and can also be recycled by a water-soluble method, so that the recycling of the catalyst is realized. Therefore, the biological coke gasification catalyst and the biological coke catalytic raw material disclosed by the invention have the advantages that the gasification activity of the biological coke is ensured, the cost of the gasification catalyst is reduced, and the popularization value is wide.
Claims (19)
1. A biocoke gasification catalyst comprising an alkali metal halide and an alkaline earth metal carbonate.
2. The biocoke gasification catalyst of claim 1, wherein the alkali metal halide is selected from one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, francium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, francium iodide, preferably one or more of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide.
3. The bio-coke gasification catalyst according to claim 1, wherein the alkaline earth metal carbonate is one or more of beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and radium carbonate, preferably one or more of magnesium carbonate and calcium carbonate.
4. The biocoke gasification catalyst of claim 1, wherein the alkali metal halide and the alkaline earth metal carbonate are in a mass ratio of 30: 1-1: 5, preferably 6: 1-1: 1.
5. a biocoke catalytic raw material comprises a biocoke raw material, alkali metal halide and alkaline earth metal carbonate.
6. The biocoke catalytic raw material according to claim 5, wherein the biocoke raw material is a solid product obtained by performing processes of pyrolysis or and liquefaction or and carbonization on agricultural residues, forestry wastes, household garbage, waste plastics, animal manure biomass.
7. The biocoke catalytic feedstock of claim 5, wherein said biocoke feedstock has a particle size of less than 2 mm.
8. Biocoke catalytic feedstock according to claim 5, wherein the alkali metal halide is selected from one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, francium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, francium iodide, preferably from one or more of sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide.
9. The biocoke catalytic raw material of claim 5, wherein the alkaline earth metal carbonate is one or more of beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate and radium carbonate, preferably one or more of magnesium carbonate and calcium carbonate.
10. The biocoke catalytic raw material according to claim 5, wherein the mass ratio of the sum of the alkali metal halide and the alkaline earth metal carbonate to the biocoke raw material is 50-4: 96-50, wherein the mass ratio of the alkali metal halide to the alkaline earth metal carbonate is 30: 1-1: 5, preferably 6: 1-1: 1.
11. the process for preparing the biocoke catalytic raw material according to any one of claims 5 to 10, wherein the biocoke catalytic raw material is obtained by mixing the biocoke raw material, alkali metal halide and alkaline earth metal carbonate, uniformly mixing and drying.
12. The process for preparing a biocoke catalytic raw material as set forth in claim 11, wherein the drying temperature is 60 to 120 ℃.
13. A process for the preparation of a biocoke catalytic feedstock as claimed in any one of claims 5 to 10, said process comprising the steps of:
(1) mixing alkali metal halide with water to prepare an alkali metal halide aqueous solution;
(2) mixing a biological coke raw material with the alkali metal halide aqueous solution obtained in the step (1), uniformly mixing, and drying to obtain the biological coke loaded with the alkali metal halide;
(3) and (3) mixing the biological coke loaded with the alkali metal halide obtained in the step (2) with the alkaline earth metal carbonate, uniformly mixing, and drying to obtain the biological coke catalytic raw material.
14. The method for preparing a biocoke catalytic raw material according to claim 13, wherein the amount of water added is 1.5 to 2g of water per g of biocoke, depending on the type of biocoke and the air humidity, as the saturated water absorption capacity of the biocoke equivalent ratio.
15. The method for preparing a biocoke catalytic raw material according to claim 13, wherein the drying temperature in the step (2) is 60 to 120 ℃.
16. The method for preparing a biocoke catalytic raw material according to claim 13, wherein the drying temperature in the step (3) is 100 to 120 ℃.
17. A process for gasifying biological coke, wherein the catalytic raw material of the biological coke as claimed in any one of claims 5 to 10 is contacted with steam in a gasification furnace to perform gasification reaction.
18. The biological coke gasification process according to claim 17, wherein the gasification reaction temperature is 700 to 950 ℃.
19. The biological char gasification process according to claim 17, wherein the mass ratio of the steam to the biological char raw material in the biological char gasification reaction process is 0.1 to 10, preferably 0.2 to 8.
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