CN115466157A - Method for co-producing methane and olefin by catalytic gasification - Google Patents
Method for co-producing methane and olefin by catalytic gasification Download PDFInfo
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- CN115466157A CN115466157A CN202210955413.XA CN202210955413A CN115466157A CN 115466157 A CN115466157 A CN 115466157A CN 202210955413 A CN202210955413 A CN 202210955413A CN 115466157 A CN115466157 A CN 115466157A
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- methane
- gasification
- olefin
- raw material
- coal
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 238000002309 gasification Methods 0.000 title claims abstract description 65
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 29
- 239000003245 coal Substances 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- 239000002893 slag Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 29
- 229910052742 iron Inorganic materials 0.000 claims description 22
- 239000002956 ash Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000010459 dolomite Substances 0.000 claims description 14
- 229910000514 dolomite Inorganic materials 0.000 claims description 14
- 239000010883 coal ash Substances 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 235000019738 Limestone Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000010450 olivine Substances 0.000 claims description 3
- 229910052609 olivine Inorganic materials 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- -1 carbon olefin Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
-
- 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
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/20—Carbon compounds
- C07C2527/232—Carbonates
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method for co-producing methane and olefin by catalytic gasification, belonging to the technical field of catalytic coal gasification. The production method comprises the steps of mixing coal raw materials and calcium or/and magnesium containing raw materials, carrying out low-temperature reaction to obtain pretreated raw materials, transferring the pretreated raw materials to a high-temperature gasification section of a gasification furnace, carrying out reaction at 700-850 ℃ to generate methane-containing synthetic gas, transferring the methane-containing synthetic gas and part of ash slag generated by the high-temperature gasification section to a low-temperature synthesis section of the gasification furnace, and carrying out reaction at 350-450 ℃ to obtain the low-carbon olefin. The invention can produce methane and low-carbon olefin simultaneously, and can flexibly adjust the output of different products according to actual requirements on the basis of cost control.
Description
Technical Field
The invention relates to a method for producing fine chemical products by coal catalysis, belongs to the technical field of coal catalytic gasification, and particularly relates to a method for co-producing methane and olefin by catalytic gasification.
Background
The catalytic coal gasification belongs to the third generation coal gasification method. The alkali metal catalyst can synchronously catalyze carbohydrate reaction, water gas shift and carbon monoxide hydrogenation methanation reaction to generate methane-rich synthesis gas. Because the income of the methane product is influenced by factors such as regions, seasons, monopoly of pipe networks and the like, the risk resistance of enterprises is reduced by taking the methane as the only product.
Coal-to-olefins is one of the routes for clean conversion of coal. The existing coal-to-olefin method generally adopts coal-to-methanol as an intermediate, and then olefin synthesis reaction is carried out, so that the route is long. The preparation of methane and the co-production of olefin by one-step coal gasification are good supplements for methane preparation from coal. The alkali metal potassium and sodium catalyst has the best gasification activity and simultaneously has good methanation activity. But the cost is high, and the catalyst in the gasified ash needs to be recycled. In order to produce methane from coal and co-produce high value-added low-carbon olefins, a low-cost and multifunctional composite catalyst system needs to be developed.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a method for co-producing methane and olefin by catalytic gasification, which can co-produce methane and low-carbon olefin by exerting the catalytic action of different catalysts, and can flexibly adjust the yield of different products according to actual requirements on the basis of cost control.
In order to realize the technical purpose, the invention discloses a method for co-producing methane and olefin by catalytic gasification, which comprises the steps of mixing a coal raw material and a calcium or/and magnesium containing raw material, carrying out low-temperature reaction to obtain a pretreated raw material, transferring the pretreated raw material to a high-temperature gasification section of a gasification furnace, carrying out reaction at 700-850 ℃ to generate a methane-containing synthetic gas, transferring the methane-containing synthetic gas and part of ash slag generated by the high-temperature gasification section to a low-temperature synthesis section of the gasification furnace, and carrying out reaction at 350-450 ℃ to obtain low-carbon olefin.
Further, the method comprises the steps of:
1) Pre-oxidation treatment: mixing the coal raw material and the calcium or/and magnesium containing raw material, and reacting for 0.5-4 h at 60-200 ℃ in an aerobic water vapor environment;
2) High-temperature gasification: placing the pretreated raw material obtained in the step 1) in a high-temperature gasification section of a gasification furnace, and reacting for 1-20 h at 750-800 ℃ to generate synthesis gas containing methane; the synthesis gas also comprises hydrogen, carbon monoxide, water vapor and the like;
3) Low-temperature synthesis: and (3) reacting the synthesis gas containing methane in the step 2) with part of generated ash at 400 ℃ to obtain the low-carbon olefin.
Further, the aerobic steam environment in step 1) is air containing steam or pure oxygen, and the oxygen concentration is above 10%, the pre-oxidation treatment is normal pressure, in the pre-oxidation treatment stage, carbon and hydrogen atoms in the coal react with oxygen to generate oxygen-containing functional groups, the oxygen concentration is above 10% to ensure sufficient reaction speed, and the oxygen concentration refers to the percentage of the volume of oxygen, and the oxygen concentration is not higher than 20%.
Further, the coal raw material is high-iron coal or non-iron coal raw material, and FeS is not added or added 2 The iron content in the mixture accounts for more than 10wt% of the coal ash content. The invention adopts high-speed rail coal or external FeS 2 This is because FeS 2 The iron in the iron has better chemical adsorption strength, can effectively adsorb oxygen, improve the concentration of adsorbed oxygen, promote the oxidation and heat release of the pyrite, improve the microenvironment temperature of carbon bonds around the pyrite, promote the directional oxidation of the carbon bonds in an active temperature interval to generate oxygen-containing functional groups, and increase the number of hydroxyl groups or carboxyl groups. And too low iron content results in a small amount of active center phase and insignificant catalytic effect.
Furthermore, the using amount of the partial ash is not particularly limited, and the mass of the partial ash is 0.01wt% of the coal ash.
Further, the lower olefin has 5 or less carbon atoms, and is preferably ethylene.
Further, the calcium or/and magnesium containing material comprises calcium or/and magnesium oxide, hydroxide or various inorganic salts, preferably dolomite, limestone, olivine and molecular sieve, and the mass of the calcium or/and magnesium containing material is 5-15 wt% of coal ash. The raw materials containing calcium or/and magnesium can effectively catalyze the coal gasification reaction, and the content of calcium and magnesium is determined by taking the catalytic activity as a standard. And the calcium or/and magnesium-containing raw material and the newly generated carboxyl and hydroxyl are subjected to ion exchange to generate a high-catalytic-activity calcium phase and/or magnesium phase for converting carbon monoxide and hydrogen into low-carbon olefin.
Furthermore, the pressure of the high-temperature gasification section is 1.5-4.0 MPa, and the pressure of the low-temperature synthesis section is 1.5-4.0 MPa.
Further, the particle size of the coal raw material is less than 3mm, and the particle size of the calcium or/and magnesium containing raw material is less than 0.4mm.
The co-production process method designed by the invention comprises pre-oxidation treatment, high-temperature gasification and low-temperature synthesis, wherein in the pre-oxidation treatment stage, the coal raw material is pre-oxidized, and meanwhile, the ion exchange load of calcium/magnesium is realized, so that a high-catalytic-activity calcium phase and/or magnesium phase can be generated.
In a high-temperature gasification section, under the catalytic action of a high-catalytic activity calcium phase and/or magnesium phase, the pretreated mixed coal sample is gasified and reacted by carbon in the coal and oxygen/steam to generate a large amount of synthesis gas containing methane and ash slag, iron in the ash slag exists in the form of oxide or simple substance iron, and is further reduced and carbonized by the mixed gas of reducing gas hydrogen and carbonized gas methane to generate iron carbide.
In the low-temperature synthesis section, the iron carbide in the ash slag effectively catalyzes the carbon monoxide and the hydrogen in the synthesis gas to generate the low-carbon olefin.
Meanwhile, the low-carbon olefin and the methane gas can be separated by a cryogenic method by utilizing different boiling points.
Compared with the prior art, the technical scheme provided by the embodiment of the invention has the following advantages:
the co-production method designed by the invention can co-produce methane and low-carbon olefin by playing the catalytic action of different catalysts generated in the reaction process, and can flexibly adjust the yield of different products according to actual requirements on the basis of cost control.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is a flow chart of a preparation process according to an embodiment of the present invention.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, a solution of the present invention will be further described below. It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The invention discloses a method for co-producing methane and olefin by catalytic gasification, which comprises the steps of mixing coal raw materials and calcium or/and magnesium containing raw materials, reacting for 0.5-4 h at 60-200 ℃ in an aerobic water vapor environment, transferring the pretreated raw materials to a high-temperature gasification section of a gasification furnace, reacting for 1-20 h at 700-850 ℃ to generate methane-containing synthesis gas, transferring the methane-containing synthesis gas and part of ash slag generated by the high-temperature gasification section to a low-temperature synthesis section of the gasification furnace, and reacting at 350-450 ℃ to obtain low-carbon olefin, as shown in figure 1. The lower olefin herein has 5 or less carbon atoms, and is preferably ethylene. Wherein the coal raw material shown in figure 1 is high-iron coal, and FeS can be added into the coal raw material without iron 2 。
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein; it is to be understood that the embodiments described in this specification are only some embodiments of the invention, and not all embodiments.
Example 1
The embodiment discloses a method for co-producing methane and olefin by catalytic gasification, which comprises the following steps:
1) Pre-oxidation treatment: mixing a high-iron coal raw material with the grain diameter of less than 3mm (the iron content accounts for 10 percent of coal ash content) and dolomite with the grain diameter of less than 0.4mm, and reacting for 0.5 to 4 hours at 60 ℃ in an aerobic steam environment (the oxygen volume fraction is 10 percent); wherein, the mass of the dolomite is 5wt% of the coal ash;
2) High-temperature gasification: placing the pretreated raw material obtained in the step 1) in a high-temperature gasification section of a gasification furnace, and reacting at 750 ℃ for 1.5h to generate synthesis gas containing methane; controlling the pressure to be 3.5MPa;
3) Low-temperature synthesis: reacting the synthesis gas containing methane in the step 2) and generated partial ash at 400 ℃ to obtain low-carbon olefin, wherein the pressure is controlled to be 2.5MPa;
in this example, the conversion of carbon in the coal feed was 85wt% and the yield of methane was 0.26Nm 3 KgC, and the mass ratio of methane to the lower olefins is 1.2.
Example 2
The embodiment discloses a method for co-producing methane and olefin by catalytic gasification, which comprises the following steps:
1) Pre-oxidation treatment: mixing a high-iron coal raw material with the grain diameter of less than 3mm (the iron content accounts for 10 percent of coal ash content) and dolomite with the grain diameter of less than 0.4mm, and reacting for 0.5 to 4 hours at 200 ℃ in an aerobic steam environment (the oxygen volume fraction is 20 percent); wherein the mass of the dolomite is 15wt% of the ash content of the coal;
2) High-temperature gasification: placing the pretreated raw material obtained in the step 1) in a high-temperature gasification section of a gasification furnace, and reacting for 2h at 750 ℃ to generate synthesis gas containing methane; controlling the pressure to be 1.5MPa;
3) Low-temperature synthesis: reacting the synthesis gas containing methane in the step 2) and part of generated ash at 400 ℃ to obtain low-carbon olefin, wherein the pressure is controlled to be 3.0MPa;
in this example, the conversion of carbon in the coal feed was 88wt% and the yield of methane was 0.28Nm 3 KgC, and the mass ratio of methane to the lower olefins is 1.
Example 3
The embodiment discloses a method for co-producing methane and olefin by catalytic gasification, which comprises the following steps:
1) Pre-oxidation treatment: mixing a high-iron coal raw material (the iron content accounts for 10% of coal ash) with the grain size of less than 3mm and dolomite with the grain size of less than 0.4mm, and reacting for 0.5-4 h at 100 ℃ in an aerobic steam environment (the oxygen volume fraction is 10%); wherein, the mass of the dolomite is 10wt% of the coal ash;
2) High-temperature gasification: placing the pretreated raw material obtained in the step 1) in a high-temperature gasification section of a gasification furnace, and reacting for 2h at 800 ℃ to generate synthesis gas containing methane; controlling the pressure to be 3.5MPa;
3) Low-temperature synthesis: reacting the synthesis gas containing methane in the step 2) and generated partial ash at 400 ℃ to obtain low-carbon olefin, wherein the pressure is controlled to be 3.5MPa;
in this example, the conversion of carbon in the coal feed was 90wt% and the yield of methane was 0.30Nm 3 KgC, and the mass ratio of methane to the lower olefins is 1.8.
Example 4
The difference from the above example 3 is that the dolomite mass is 15wt% of the coal ash.
In this example, the conversion of carbon in the coal feed was 96wt% and the yield of methane was 0.25Nm 3 KgC, and the mass ratio of methane to the lower olefins is 1.
Example 5
The difference from the above example 3 is that the dolomite mass is 10wt% of the coal ash.
In this example, the conversion of carbon in the coal feed was 92wt% and the yield of methane was 0.23Nm 3 KgC, and the mass ratio of methane to the lower olefins is 1.
Example 6
The difference from example 5 above is that dolomite is replaced with limestone.
In this example, the conversion of carbon in the coal feed was 90wt% and the yield of methane was 0.25Nm 3 KgC, and the mass ratio of methane to the lower olefins is 1.
Example 7
The difference from example 5 above is that dolomite is replaced with olivine.
In this example, the conversion of carbon in the coal feed was 88wt% and the yield of methane was 0.20Nm 3 KgC, and the mass ratio of methane to the lower olefins is 1.
Example 8
The difference from example 5 above is that dolomite is replaced with molecular sieve LTA.
In this example, the conversion of carbon in the coal feed was 80wt% and the yield of methane was 0.18Nm 3 KgC, and the mass ratio of methane to the lower olefins is 1.
In conclusion, the invention controls the output ratio of methane and olefin by controlling the types and the addition amounts of the raw materials of calcium and magnesium, the temperature of the high-temperature reaction section, the temperature of the low-temperature synthesis section, the gasification reaction time and the reaction pressure.
Comparative example 1
Unlike example 5 above, the pre-oxidation treatment of step 1) was not performed, and as a result, it was found that no catalytically active phase was formed, resulting in a decrease in the carbon conversion of the coal gasification reaction, as low as 50wt% or less.
Comparative example 2
Unlike example 5 above, the reaction was carried out in one step in a high temperature gasification stage at 450 to 650 ℃, and as a result, it was found that olefins could not be produced and the carbon conversion rate decreased.
Comparative example 3
Unlike example 5, the process of using a coal material containing no iron and adding no ferrous sulfide resulted in no olefin synthesis catalyst, resulting in no olefin production in the produced gas.
Comparative example 4
Different from the above example 5, the method adopts a coal raw material without iron, but adds ferrous sulfide with the same iron content as that of the example 5 to finally prepare methane and low-carbon olefin;
in this example, the conversion of carbon in the coal feed was 92wt% and the yield of methane was 0.23Nm 3 KgC, and the mass ratio of methane to the lower olefins is 1.8.
Comparative example 5
In contrast to example 5 above, the conversion of carbon was found to be less than 50% by weight when sodium silicate was used instead of dolomite.
Comparative example 6
The operation of example 5 was repeated by using the ash obtained finally in the low-temperature synthesis stage of example 5, and the ash was reused more than 10 times. The result shows that the ash can still produce methane and low carbon olefin when used more than 10 times.
And the gas generation conditions of the above examples and comparative examples are shown in the following table 1;
gas generation lists for examples 1 to 8 and comparative examples 1 to 6
And the lower olefins in table 1 above are mainly ethylene, and may further contain a small amount of propylene, butene, etc.
Therefore, the synthesis process designed by the invention is crucial to the generation of olefin in the produced gas. The synthesis process designed by the invention can realize flexible adjustment of the mass ratio of methane to low-carbon olefin.
In conclusion, the co-production method designed by the invention can co-produce methane and low-carbon olefin by playing the catalytic action of different catalysts generated in the reaction process, and can flexibly adjust the yield of different products according to actual requirements on the basis of cost control.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising one of 8230; \8230;" 8230; "does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
The above description is merely illustrative of particular embodiments of the invention that enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for co-producing methane and olefin by catalytic gasification is characterized by comprising the steps of mixing a coal raw material and a calcium or/and magnesium containing raw material, carrying out low-temperature reaction to obtain a pretreated raw material, transferring the pretreated raw material to a high-temperature gasification section of a gasification furnace, carrying out reaction at 700-850 ℃ to generate a methane-containing synthetic gas, transferring the methane-containing synthetic gas and part of ash slag generated by the high-temperature gasification section to a low-temperature synthesis section of the gasification furnace, and carrying out reaction at 350-450 ℃ to obtain low-carbon olefin.
2. The catalytic gasification process for co-producing methane and olefins according to claim 1, comprising the steps of:
1) Pre-oxidation treatment: mixing the coal raw material and the calcium or/and magnesium containing raw material, and reacting for 0.5-4 h at 60-200 ℃ in an aerobic water vapor environment;
2) High-temperature gasification: placing the pretreated raw material obtained in the step 1) in a high-temperature gasification section of a gasification furnace, and reacting for 1-20 h at 750-800 ℃ to generate synthesis gas containing methane;
3) Low-temperature synthesis: and (3) reacting the synthesis gas containing methane in the step 2) with part of generated ash at 400 ℃ to obtain the low-carbon olefin.
3. The catalytic gasification process for co-producing methane and olefin according to claim 2, wherein the aerobic steam environment in step 1) is air containing water vapor or pure oxygen, and the oxygen concentration is 10% or more and not more than 20%.
4. The method for co-producing methane and olefin through catalytic gasification according to any one of claims 1-3, wherein the coal raw material is high-iron coal or non-iron coalRaw material adopting FeS without addition and/or addition 2 The iron content in the mixture accounts for more than 10wt% of the coal ash content.
5. The method for co-producing methane and olefin through catalytic gasification according to claim 4, wherein the number of carbon atoms of the low-carbon olefin is less than or equal to 5.
6. The catalytic gasification process for co-producing methane and olefins according to claim 4, wherein the lower olefins are ethylene.
7. The method for co-producing methane and olefin through catalytic gasification according to claim 1, 2, 3, 5 or 6, wherein the calcium or/and magnesium-containing raw material comprises calcium or/and magnesium oxide, hydroxide or various inorganic salts, and the mass of the calcium or/and magnesium-containing raw material is 5-15 wt% of coal ash.
8. The catalytic gasification process for co-producing methane and olefin according to claim 7, wherein the calcium or/and magnesium-containing raw material is one or more of dolomite, limestone, olivine and molecular sieve.
9. The method for co-producing methane and olefin by catalytic gasification according to claim 1, 2, 3, 5, 6 or 8, wherein the pressure of the high-temperature gasification section is 1.5-4.0 MPa, and the pressure of the low-temperature synthesis section is 1.5-4.0 MPa.
10. The catalytic gasification process for co-producing methane and olefins according to claim 1 or 2 or 3 or 5 or 6 or 8, wherein the coal feedstock has a particle size of less than 3mm and the calcium or/and magnesium containing feedstock has a particle size of less than 0.4mm.
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CN102465047A (en) * | 2010-11-02 | 2012-05-23 | 新奥科技发展有限公司 | Method for preparing methane by catalyzing and gasifying coal |
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CN102465047A (en) * | 2010-11-02 | 2012-05-23 | 新奥科技发展有限公司 | Method for preparing methane by catalyzing and gasifying coal |
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