CN115180593A - Method for preparing high-added-value product by reforming light-driven co-thermal coupling hydrocarbons from carbonate refining - Google Patents
Method for preparing high-added-value product by reforming light-driven co-thermal coupling hydrocarbons from carbonate refining Download PDFInfo
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- CN115180593A CN115180593A CN202210684268.6A CN202210684268A CN115180593A CN 115180593 A CN115180593 A CN 115180593A CN 202210684268 A CN202210684268 A CN 202210684268A CN 115180593 A CN115180593 A CN 115180593A
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- carbonate
- alkane
- catalyst
- gas
- carbon dioxide
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000002407 reforming Methods 0.000 title claims abstract description 19
- 238000007670 refining Methods 0.000 title claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 9
- 230000008878 coupling Effects 0.000 title abstract description 17
- 238000010168 coupling process Methods 0.000 title abstract description 17
- 238000005859 coupling reaction Methods 0.000 title abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 17
- 239000010453 quartz Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 14
- 239000001095 magnesium carbonate Substances 0.000 claims description 14
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 229910000510 noble metal Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000013032 photocatalytic reaction Methods 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims description 2
- 229910000003 Lead carbonate Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- 229910000011 cadmium carbonate Inorganic materials 0.000 claims description 2
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 14
- 238000006057 reforming reaction Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 20
- 235000014380 magnesium carbonate Nutrition 0.000 description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910017727 AgNi Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- -1 refractory Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
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- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
- C01F11/04—Oxides or hydroxides by thermal decomposition
- C01F11/06—Oxides or hydroxides by thermal decomposition of carbonates
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- C01G9/03—Processes of production using dry methods, e.g. vapour phase processes
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
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- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
- C04B2/102—Preheating, burning calcining or cooling of magnesia, e.g. dead burning
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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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Abstract
The invention discloses a method for preparing high value-added products by reforming light-driven carbonate refining co-thermal coupling hydrocarbons. The method is characterized in that the metal oxide can be obtained at a lower reaction temperature by refining the carbonate with alkane; the carbon dioxide released in the carbonate pyrolysis process is utilized while the co-heat generated by the carbonate pyrolysis is utilized to carry out alkane co-thermal coupling reforming, so that a product with a high added value is obtained, the emission reduction of the carbon dioxide in the traditional carbonate refining process is realized, and the greenhouse effect is favorably relieved; and different types of high-efficiency Ni-based monatomic alloy catalysts are prepared, and compared with the simple substance Ni catalyst, the alkane reforming reaction is driven under a milder condition, so that the thermodynamic energy barrier in the alkane reforming reaction is reduced, the catalytic efficiency is greatly improved, excessive oxidation inactivation of the catalyst is avoided, and the energy consumption cost of the alkane dry reforming reaction is favorably reduced. The invention can realize the aims of carbon emission reduction and energy consumption reduction, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of preparing metal oxide by carbonate, and particularly relates to a method for preparing a high-added-value product by reforming co-thermal coupling hydrocarbons through light-driven carbonate refining.
Background
The heavy process industries such as cement, steel, refractory, calcium carbide and the like are important supporting industries for national economic development. Carbonates are among the common raw materials required by such process industries, including limestone (CaCO) 3 ) Magnesite (MgCO) 3 ) Dolomite (CaMg (CO) 3 ) 2 ) And the carbonate is thermally decomposed at high temperature to form metal oxide which is used as a basic raw material in national economy and can be used for subsequent production. However, the pyrolysis of carbonate discharges a large amount of carbon dioxideThe emission of carbon dioxide from the process industry associated with heavy emissions exceeds 50% of the total carbon emissions from the national industry. How to convert carbon dioxide in situ in the carbonate refining process and make the carbon dioxide further utilized becomes a problem to be solved urgently in the current carbonate refining industry. In addition, how to use clean energy such as light energy in the traditional industry to further reduce the production cost has great significance. Solar-driven catalytic reactions have high selectivity under mild reaction conditions, which provides an alternative green sustainable development approach for energy conversion and storage, and is one of the more promising and practical solutions to current and future global energy and environmental issues.
Disclosure of Invention
The invention provides a light-driven method for reforming carbonate refining co-thermal coupling hydrocarbons to prepare high value-added products, which is used for carbon dioxide emission reduction and aims to overcome the defect that a large amount of carbon dioxide is generated in the traditional process of preparing oxides by decomposing carbonate.
The method for preparing the high added value product by reforming the light-driven carbonate refining co-thermal coupling hydrocarbons comprises the following steps: placing a quartz tube in a photo-thermal reaction furnace, placing carbonate on the left side of the quartz tube, introducing alkane gas from an opening on the left side of the quartz tube, and heating and decomposing the carbonate in alkane atmosphere to obtain solid metal oxide and carbon dioxide gas; a catalyst is arranged on the right side of the quartz tube, a light source is applied above the catalyst for irradiation, and carbon dioxide gas obtained by decomposing alkane and carbonate undergoes a photocatalytic reaction under the action of the catalyst to obtain a high value-added chemical.
The diameter of the quartz tube is contracted to 30-80% of the original diameter at the middle position of the left side where the carbonate is placed and the right side where the catalyst is placed.
The carbonate is any one or more of calcium carbonate, magnesium carbonate, iron carbonate, barium carbonate, cadmium carbonate, zinc carbonate, lead carbonate or copper carbonate.
The heating temperature of the carbonate in the alkane atmosphere is 300-800 ℃, the heating rate is 1-100 ℃/min, and the heating time is 1-200min.
The alkane gas is methane and/or ethane; the gas space velocity of alkane gas to carbonate is 10000-1000000 mL/g.h, and the pressure of alkane gas is normal pressure-10 MPa.
Nitrogen or inert gas is doped into the alkane gas, and the doping amount is less than or equal to 99 percent.
The volume concentration of carbon dioxide in the photocatalytic reaction of the carbon dioxide gas obtained by decomposing the alkane and the carbonate under the action of the catalyst is 1-50%.
The light source is a xenon lamp or sunlight.
The illumination intensity of the light source is 0.1-100W/cm 2 。
The catalyst is a Ni-based monatomic alloy catalyst.
The light condition of the photocatalytic reaction is replaced by a heating condition.
The Ni-based single-atom alloy catalyst also contains one or more of noble metals Rh, ru, au, ag and Pd; metallic Ni as active component, noble metal as assistant and Al as carrier 2 O 3 、MgO、TiO 2 And/or ZnO; the mass percent of Ni is 1-50%, and the mass percent of noble metal is 0.1-10%; the particle size of Ni is 3-15nm.
The preparation method of the Ni-based monatomic alloy catalyst comprises the following steps: dissolving soluble nickel salt, soluble trivalent metal salt and soluble noble metal salt in CO 2 Obtaining mixed salt solution in water; dissolving sodium hydroxide in CO 2 Obtaining an alkali solution in water; in N 2 Under the atmosphere, simultaneously dropwise adding the mixed salt solution and the alkali solution into deionized water, continuously stirring, and controlling the pH value to be 8-12; stirring for 30-120 min after the dropwise addition, centrifuging the obtained mixed solution, and removing CO 2 Washing the precipitate with water until the pH of the supernatant is 7; and (3) carrying out rotary evaporation, drying and grinding on the obtained precipitate, and finally carrying out reduction roasting in a reduction atmosphere.
The soluble trivalent metal salt is one or more of aluminum salt, ferric salt and cobalt salt.
The soluble noble metal salt is one or more of chloride salts of Rh, ru, au, ag and Pd.
The dropping speed is 5-20rpm.
After the dropwise addition is finished, the temperature is kept between normal temperature and 60 ℃ during the stirring for 30-120 minutes.
The temperature of the rotary steaming drying is 30-60 ℃, the vacuum degree is lower than-0.1 Mpa, and the rotary steaming is continued for 30-60 minutes after the precipitation drying.
The temperature of the reduction roasting is 400-800 ℃, the flow rate of the reduction gas is 20-100mL/min, and the heating rate is 2-10 ℃/min.
The invention discloses a method for preparing a high-added-value product by reforming co-thermal coupling hydrocarbons through light-driven carbonate refining for carbon dioxide emission reduction, wherein metal oxides can be obtained at a lower reaction temperature through refining carbonates through alkanes; the carbon dioxide released in the carbonate pyrolysis process is utilized while the co-heat generated by the carbonate pyrolysis is utilized to carry out alkane co-thermal coupling reforming, so that a product with a high added value is obtained, the emission reduction of the carbon dioxide in the traditional carbonate refining process is realized, and the greenhouse effect is favorably relieved; compared with the simple substance Ni catalyst, the high-efficiency Ni-based monatomic alloy catalyst of different types is prepared, the alkane reforming reaction is driven under a milder condition, the thermodynamic energy barrier in the alkane reforming reaction is reduced, the catalytic efficiency is greatly improved (by 5-6 times), the excessive oxidation inactivation of the catalyst is avoided, and the energy consumption cost of the alkane dry reforming reaction process is favorably reduced. The invention can realize the aims of carbon emission reduction and energy consumption reduction, and has wide application prospect.
Drawings
FIG. 1 is a schematic diagram of the principle of the process for producing synthesis gas by co-thermal coupling methane reforming in light-driven carbonate refining in example 1;
FIG. 2 scanning electron micrographs of magnesium carbonate in example 1;
FIG. 3 scanning electron micrograph of magnesium oxide after pyrolysis reaction in example 1;
FIG. 4X-ray diffraction pattern of magnesium carbonate of example 1 and magnesium oxide after pyrolysis;
FIG. 5 high resolution picture of RuNi monatomic alloy in example 1;
FIG. 6 is a graph of the performance results of pure Ni and RuNi as catalysts in example 1;
FIG. 7 is a high resolution picture of AgNi monatomic alloy;
FIG. 8 is a high resolution picture of RhNi single atom alloy;
FIG. 9 is a schematic diagram of the principle of the process for producing ethylene by co-thermal coupling ethane reforming in light-driven carbonate refinery in example 2;
FIG. 10 gas chromatography analysis of the gaseous products of example 2;
FIG. 11 is a schematic diagram of the principle of the method for producing high value-added products by reforming light-driven carbonate refinery co-thermal coupling hydrocarbons.
Detailed Description
Example 1
RuNi catalyst preparation: dissolving nickel chloride, aluminum chloride and ruthenium chloride in CO 2 Obtaining mixed salt solution in water; dissolving sodium hydroxide in CO 2 Obtaining an alkali solution in water; in N 2 Under the atmosphere, the mixed salt solution and the alkali solution are simultaneously dripped into deionized water, the dripping speed is 20rpm, the stirring is continuously carried out, and the pH value is controlled to be 10; stirring for 100 min at normal temperature after the dropwise addition is finished, centrifuging the obtained mixed solution, and then removing CO 2 Washing the precipitate with water until the pH of the supernatant is 7; rotary steaming the obtained precipitate at 60 deg.C under vacuum degree of-0.1 Mpa for 60 min; grinding the precipitate, and finally carrying out reduction roasting at 400 ℃ in a hydrogen atmosphere, wherein the gas flow rate is 80mL/min, and the heating rate is 5 ℃/min. In the prepared Ni-based monatomic RuNi alloy catalyst, metallic Ni is used as an active component, ru is used as an auxiliary agent, and a carrier is Al 2 O 3 (ii) a The mass percent content of Ni is 1 percent, and the mass percent content of noble metal is 0.1 percent.
As shown in fig. 1, the specific steps of co-thermal coupling methane reforming to synthesis gas by light-driven magnesium carbonate refining are as follows: placing the quartz tube in a photo-thermal reaction furnace, and shrinking the diameter of the quartz tube to 50% of the original diameter; 100mg of magnesium carbonate is paved at the left side of a closing-in opening in a quartz tube, 10mg of the RuNi catalyst prepared above is paved at the right side of the closing-in opening, methane flows in from the left opening of the quartz tube at the flow rate of 40mL/min, the pyrolysis temperature is set to be 400 ℃, the temperature rise time is set to be 30min, the reaction time is set to be 90min, and a magnesium oxide product can be obtained after roasting. A xenon lamp is arranged above the RuNi catalyst for irradiation, carbon dioxide obtained in the methane and magnesium carbonate pyrolysis process is subjected to co-thermal coupling reforming under the action of RuNi monatomic alloy, and a gas product is subjected to online detection by using a gas phase.
FIG. 2 is a scanning electron micrograph of magnesium carbonate, and FIG. 3 is a scanning electron micrograph of magnesium oxide obtained after pyrolysis reaction. As can be seen from the figure, magnesium carbonate before the reaction is a massive solid in CH 4 Pyrolyzing at 400 ℃ in the atmosphere to obtain the magnesia which is still a blocky solid. In fig. 4, two data lines from bottom to top are X-ray diffraction patterns of magnesium carbonate and magnesium oxide after pyrolysis reaction. Can find at CH 4 After pyrolysis at 400 ℃ in the atmosphere, magnesium carbonate is completely converted into magnesium oxide. FIG. 5 is a high resolution picture of RuNi monatomic alloy catalyst prepared, with good Ru dispersion, exposing the (111) crystal plane of Ni. The performance results of the coupled reforming obtained gas product are shown in FIG. 6, where the gas product is H 2 And CO, the addition of Ru greatly increased the syngas yield (by approximately 5-6 times) compared to the elemental Ni catalyst. In Ni-based catalysts, different noble metals such as Ag, rh are incorporated, and different products (HCOOH, C) are obtained 2 H 6 Etc.). Fig. 7 and 8 are high resolution pictures of the AgNi and RhNi monoatomic alloys, respectively, with Ag or Rh dispersed well, both alloys exposing the (111) crystal plane of Ni.
Example 2
As shown in fig. 9, the specific steps of co-thermal coupling ethane reforming for light-driven magnesium carbonate refining are as follows: placing the quartz tube in a photo-thermal reaction furnace, and shrinking the diameter of the middle of the quartz tube to 50% of the original diameter; spreading 100mg of magnesium carbonate at the left side of a closed opening in a quartz tube, spreading 10mg of RuNi catalyst at the right side of the closed opening, setting the ethane flow rate at 30mL/min, the pyrolysis temperature at 400 ℃, the temperature rise time at 30min, and the reaction time at 120 min, and roasting to obtain a magnesium oxide product; xenon lamp irradiation is arranged above the RuNi catalyst, ethane and carbon dioxide obtained in the pyrolysis process are subjected to coupling reforming under the action of RuNi single-atom alloy, and products are subjected to online detection by using a gas phase. The detection result is shown in fig. 10, and the gas product contains ethylene and a small amount of synthesis gas; it is demonstrated that the production of high value-added ethylene is achieved by co-thermal coupling reforming of ethane and carbon dioxide produced by pyrolysis of carbonates.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing high added value products by reforming thermally coupled hydrocarbons in light-driven carbonate refining is characterized by comprising the following steps: placing a quartz tube in a photo-thermal reaction furnace, placing carbonate on the left side of the quartz tube, introducing alkane gas from an opening on the left side of the quartz tube, and heating and decomposing the carbonate in alkane atmosphere to obtain solid metal oxide and carbon dioxide gas; and a catalyst is arranged on the right side of the quartz tube, a light source is applied to irradiate the catalyst, and the alkane and carbon dioxide gas obtained by decomposing carbonate undergo a photocatalytic reaction under the action of the catalyst to obtain a high value-added chemical.
2. A method according to claim 1, wherein the quartz tube is contracted to a diameter of 30-80% of the original tube diameter at a position between the left side where the carbonate is placed and the right side where the catalyst is placed.
3. The method according to claim 1, wherein the carbonate is any one or more of calcium carbonate, magnesium carbonate, iron carbonate, barium carbonate, cadmium carbonate, zinc carbonate, lead carbonate or copper carbonate; the heating temperature of the carbonate in the alkane atmosphere is 300-800 ℃, the heating rate is 1-100 ℃/min, and the heating time is 1-200min.
4. The method of claim 1, wherein the alkane gas is methane and/or ethane; the gas space velocity of alkane gas to carbonate is 10000-1000000 mL/g.h, and the pressure of alkane gas is normal pressure-10 MPa; the volume concentration of carbon dioxide in the photocatalytic reaction of the carbon dioxide gas obtained by decomposing the alkane and the carbonate under the action of the catalyst is 1-50%.
5. The method of claim 1, wherein the light source is a xenon lamp or sunlight; the illumination intensity of the light source is 0.1-100W/cm 2 。
6. The method of claim 1, wherein the catalyst is a Ni-based monatomic alloy catalyst.
7. The method according to claim 6, wherein the Ni-based monatomic alloy catalyst further contains one or more of noble metals Rh, ru, au, ag, pd; metallic Ni as active component, noble metal as assistant and Al as carrier 2 O 3 、MgO、TiO 2 And/or ZnO; the mass percent of Ni is 1-50%, and the mass percent of noble metal is 0.1-10%; the particle size of Ni is 3-15nm.
8. The method according to claim 7, wherein the Ni-based monatomic alloy catalyst is prepared by: dissolving soluble nickel salt, soluble trivalent metal salt and soluble noble metal salt in CO 2 Obtaining mixed salt solution in water; dissolving sodium hydroxide in CO 2 Obtaining an alkali solution in water; in N 2 Under the atmosphere, simultaneously dropwise adding the mixed salt solution and the alkali solution into deionized water, continuously stirring, and controlling the pH value to be 8-12; stirring for 30-120 min after finishing the dripping, centrifuging the obtained mixed solution, and then removing CO 2 Washing the precipitate with water until the pH of the supernatant is 7; and (3) carrying out rotary evaporation, drying and grinding on the obtained precipitate, and finally carrying out reduction roasting in a reduction atmosphere.
9. The method according to claim 8, wherein the soluble trivalent metal salt is one or more of aluminum salt, iron salt and cobalt salt; the soluble noble metal salt is one or more of chloride salts of Rh, ru, au, ag and Pd.
10. The method of claim 8, wherein the temperature of the reduction roasting is 400-800 ℃, the flow rate of the reduction gas is 20-100mL/min, and the temperature rise rate is 2-10 ℃/min.
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