CN110898823A - Magnesium aluminate spinel catalyst and application thereof in desulfurization field - Google Patents
Magnesium aluminate spinel catalyst and application thereof in desulfurization field Download PDFInfo
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- CN110898823A CN110898823A CN201911256362.6A CN201911256362A CN110898823A CN 110898823 A CN110898823 A CN 110898823A CN 201911256362 A CN201911256362 A CN 201911256362A CN 110898823 A CN110898823 A CN 110898823A
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- magnesium aluminate
- aluminate spinel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 239000011777 magnesium Substances 0.000 title claims abstract description 57
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 55
- 239000011029 spinel Substances 0.000 title claims abstract description 54
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 51
- -1 Magnesium aluminate Chemical class 0.000 title claims abstract description 49
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 9
- 230000023556 desulfurization Effects 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 159000000003 magnesium salts Chemical class 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 26
- 239000007789 gas Substances 0.000 abstract description 23
- 239000011593 sulfur Substances 0.000 abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 abstract description 16
- 230000003647 oxidation Effects 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 3
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 abstract 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000001816 cooling Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000010718 Oxidation Activity Effects 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052566 spinel group Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- 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
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
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Abstract
The invention discloses a magnesium aluminate spinel catalyst and application thereof in the field of desulfurization. The catalyst takes an organic solvent as an oxygen donor and a solvent, a magnesium aluminate spinel precursor is synthesized by a hydrothermal method, and the magnesium aluminate spinel catalyst is obtained by high-temperature roasting. In the roasting process, the organic components in the precursor are combusted and discharged in a gas form, so that the synthesis temperature is reduced, and the synthesized catalyst has proper pore size distribution and larger specific surface area. The invention is the first timeApplication of magnesium aluminate spinel to hydrogen sulfide (H)2S) selective oxidation field and carbonyl sulfide (COS) oxidation field. At a lower reaction temperature, the prepared magnesia-alumina spinel catalyst is used in H2Higher H in S selective oxidation reaction2S conversion and product sulfur selectivity. The catalyst has better COS one-step removal capability and high stability.
Description
Technical Field
The invention relates to a preparation method of magnesium aluminate spinel and research on desulfurization performance of the magnesium aluminate spinel, in particular to H2A catalyst with double functions of S selective oxidation and COS oxidation and a preparation method thereof.
Background
In the chemical production processes of petrochemical industry, coal chemical industry, natural gas chemical industry and the like, a large amount of inorganic sulfur gas (as H) is generated2S is the main component) and organic sulfur gas (COS is the main component), the emission of sulfur-containing gas not only seriously pollutes the environment, but also causes great harm to human health. In addition, sulfides in industrial gas sources, whether in gas or solution form, are extremely corrosive to pipelines and production facilities. Due to environmental demands, the sulfur-containing gas must be disposed of before it can be vented to the atmosphere.
The Claus process recovers elemental sulfur from sulfur-containing gases, which is currently the most widely used desulfurization technique. However, due to thermodynamic limitations, the tail gas still contains 3-5% of H2S is not completely removed. To address this problem, one can selectively oxidize H at 100% of theoretical2The technology of S into elemental sulfur becomes a hotspot of research. The reaction equations involved therein are as follows (equilibrium 1 is the main reaction, and equilibrium 2 and 3 are side reactions):
H2s is selectively catalyzed and oxidized, the reaction is not limited by thermodynamic equilibrium, the process is simple, and the cost of device construction and operation is low. And the reaction is exothermic, and the energy consumption is low. The above characteristics indicate that H2The selective oxidation of S into elemental sulfur has good application prospect. Alumina (Al)2O3) Rich resources, stability, no toxicity, rich acid sites on the surface, in H2The field of S selective oxidation has made a certain progress. But their catalytic activity is often unsatisfactory. Iron oxide (Fe)2O3) Has higher oxidation activity and is H with the widest industrial application2S selective oxidation catalysts, but have low sulfur selectivity due to the need for excess oxygen. Therefore, the development of a high-efficiency and high-selectivity catalyst is a major research point.
The hydrolysis method is one of the most effective methods for removing COS at present. Firstly, hydrolyzing COS to H which is easier to remove by hydrolysis reaction2S gas, and then removing generated H through a desulfurizing agent2And S. This requires a series of process combinations due to the need for subsequent H removal2S, the equipment investment and the operation cost are relatively high. In addition, the high water consumption and the high sewage discharge of the process also limit the further application in the coal chemical industry. Based on the method, under the anhydrous condition, the COS is directly catalyzed and oxidized into elemental sulfur, and the one-step removal of the COS is realized.
Magnesium aluminate spinel with MgO and Al2O3The two metal oxides have the advantages of two oxides, and have new advantages which are not possessed by the two oxides, such as high thermal stability, high hydration resistance, simultaneously having two active centers of acidity and alkalinity, stable property, difficult sintering, large specific surface area and more exposed active sites, thus being H with great potential2S selective oxidation and COS one-step oxidation catalysts, but at present, the application of magnesium aluminate spinel in the field is not reported and researched.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and providesA novel preparation method of magnesium aluminate spinel and application thereof in the field of desulfurization, solving the problem of H in the prior art2The S selective oxidation catalyst has the problems of low activity, poor selectivity and stability and the like, and simultaneously solves the defects of complicated process for removing COS and the like. The prepared magnesia-alumina spinel catalyst is used for removing COS through one-step oxidation at a lower temperature, and H is selectively catalyzed and oxidized at the same time2The S aspect has higher catalytic activity and selectivity.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the preparation method of the magnesium aluminate spinel takes soluble magnesium salt and soluble aluminum salt as raw materials, takes an organic solvent as an oxygen donor and a solvent, and prepares the magnesium aluminate spinel by a hydrothermal method, wherein the mass ratio of the soluble magnesium salt to the soluble aluminum salt is 2: 1-1: 4.
Preferably, the soluble magnesium salt is MgCl2、Mg(NO3)2、MgSO4One or more of them.
Preferably, the soluble aluminum salt is one or more of tert-butyl alcohol aluminum, aluminum isopropoxide and aluminum triethoxide.
Preferably, the organic solvent and the oxygen donor are one or more of absolute ethyl alcohol, absolute isopropyl alcohol and absolute isopropyl ether.
The preparation method of the magnesium aluminate spinel specifically comprises the following steps:
and step A, weighing soluble magnesium salt and soluble aluminum salt according to a proportion, adding the soluble magnesium salt and the soluble aluminum salt into an organic solvent, and stirring the obtained mixed solution at room temperature for 2-24 hours.
B, transferring the mixed solution prepared in the step A into a hydrothermal kettle, and performing hydrothermal treatment at 130-180 ℃ for 6-18 h;
c, dropwise adding an acid solution into the product prepared in the step B, adjusting the pH value to 4-6, and magnetically stirring for 0.5-2 hours;
and D, centrifuging and drying the product prepared in the step C to obtain the magnesia-alumina spinel precursor.
And E, roasting the precursor prepared in the step D at the temperature of 600-900 ℃ to obtain the magnesium aluminate spinel catalyst.
Preferably, in the step A, the volume of the organic solvent is 50-80 mL.
Preferably, in the step C, the acid solution is HCl or HNO3、H2SO4The concentration of one or more of the (B) is 0.5-1.5 mol/L, and the dropping amount is 5-10 mL.
Preferably, in the step D, the drying temperature is 60-120 ℃, and the drying time is 6-18 h.
Preferably, in the step E, the roasting time is 6-18 h, and the temperature rise rate in the roasting process is 4-6 ℃/min.
The application of the magnesium aluminate spinel comprises the following specific steps:
the catalyst is used in H2S selective oxidation reaction, wherein the reaction temperature is 90-270 ℃, the pressure is normal pressure, and the volume space velocity is 12000-18000 h–1。
Preferably, the catalyst is used for COS oxidation reaction, the reaction temperature is 30-170 ℃, the pressure is normal pressure, and the volume space velocity is 12000-24000 h–1。
The invention has the following advantages and beneficial effects:
1. the invention applies the magnesium aluminate spinel material in the field of desulfurization, which is in H2The S selective oxidation reaction and the COS oxidation reaction have good activity, so that the application range of the magnesium-aluminum spinel material is greatly widened, and a new idea is provided for the development of a novel desulfurization catalyst.
2. The magnesium aluminate spinel synthesized catalyst has a sheet structure, mesopores are uniformly distributed on the sheet surface, and the specific surface area is 100-150 m2The rich pore structure is more beneficial to the dispersion of active components, the phenomena of pore collapse, pore blockage and the like are not easy to occur, the raw materials are low in price, the preparation process is simple, the industrial production is easy to realize, and the preparation method has a wide application prospect;
3. the porous flaky magnesium aluminate spinel material prepared by the invention does not need to load or add other active components, and the acid-base sites and oxygen vacancies contained in the porous flaky magnesium aluminate spinel material can be used as active sites for catalytic reaction.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is XRD patterns corresponding to catalysts A to D in examples 1 to 3 of the present invention and comparative example 1;
FIG. 2 is SEM images of a precursor (a) and a calcined (B) of a magnesia-alumina spinel catalyst B prepared in example 2 of the invention;
FIG. 3 shows catalysts A to E in H in examples 1 to 3 and comparative examples 1 and 2 of the present invention2H in S selective catalytic oxidation2(ii) a plot of S conversion;
FIG. 4 shows catalysts A to E in H in examples 1 to 3 and comparative examples 1 and 2 of the present invention2S selective catalytic oxidation reaction sulfur selectivity curve diagram;
FIG. 5 shows catalysts A to E in H in examples 1 to 3 and comparative examples 1 and 2 of the present invention2S selective catalytic oxidation reaction sulfur simple substance yield curve chart;
FIG. 6 shows catalyst B prepared in example 2 of the present invention, test H2S is a graph of the stability of the selective catalytic oxidation reaction;
FIG. 7 is a COS conversion rate graph of catalysts in examples 1-3 and comparative examples 2 and 3 of the present invention during the oxidation reaction of COS;
FIG. 8 shows H in the oxidation reaction of COS in catalysts of examples 1-3 and comparative examples 2 and 3 of the present invention2S concentration curve graph;
FIG. 9 is a graph showing the COS conversion rate of catalyst B prepared in example 2 of the present invention tested for stability of the oxidation reaction of COS;
FIG. 10 is H for testing COS oxidation stability of catalyst B prepared in example 2 of the present invention2S concentration profile.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to the embodiments and the accompanying drawings, which are used for further description of the present invention and are not intended to limit the present invention.
Example 1
Weighing 3.829g of aluminum isopropoxide, 4.807g of magnesium nitrate and 75mL of ethanol, mixing the mixture at room temperature for 15h by magnetic stirring, transferring the solution into a 100mL high-pressure reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 12h, then naturally cooling at room temperature, adding 5mL of 1mol/L dilute nitric acid after cooling, carrying out magnetic stirring for 2h, centrifuging, drying the precipitate at 100 ℃ for 12h, and roasting at 750 ℃ for 12h to obtain a final product, namely magnesium aluminate spinel, wherein the mark is Mg1Al1O, namely the catalyst A.
Example 2
Weighing 5.106g of aluminum isopropoxide, 3.205g of magnesium nitrate and 75mL of ethanol, mixing the mixture at room temperature for 12h by magnetic stirring, transferring the solution into a 100mL high-pressure reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 12h, then naturally cooling at room temperature, adding 5mL of 1mol/L dilute nitric acid after cooling, carrying out magnetic stirring for 2h, centrifuging, drying the precipitate at 100 ℃ for 12h, and roasting at 750 ℃ for 12h to obtain a final product, namely, magnesium aluminate spinel marked as Mg1Al2O, namely the catalyst B.
Example 3
Weighing 5.744g of aluminum isopropoxide, 2.403g of magnesium nitrate and 75mL of ethanol, mixing the mixture at room temperature for 12h by magnetic stirring, transferring the solution into a 100mL high-pressure reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 12h, then naturally cooling at room temperature, adding 5mL of 1mol/L dilute nitric acid after cooling, carrying out magnetic stirring for 2h, centrifuging, drying the precipitate at 100 ℃ for 12h, and roasting at 750 ℃ for 12h to obtain a final product, namely magnesium aluminate spinel, wherein the mark is Mg1Al3O, i.e. the catalyst C.
Comparative example 1
Weighing 7.659g of aluminum isopropoxide, mixing with 75mL of ethanol, magnetically stirring at room temperature for 12h, transferring the solution into a 100mL high-pressure reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 12h, naturally cooling at room temperature, cooling, adding 5mL of 1mol/L dilute nitric acid, magnetically stirring for 2h, centrifuging, drying the precipitate at 100 ℃ for 12h, and roasting at 750 ℃ for 12h to obtain the final product, namely aluminum oxide, and marking as D.
Comparative example 2
Commercial light MgO, labeled E, was used.
Comparative example 3
By commercial K2CO3/γ-Al2O3Labeled as F.
And (3) characterization and analysis:
x-ray powder diffraction (XRD) was measured using an X 'pertpro powder diffractometer from Panalytical to determine the phase composition of the catalyst, the detector was an X' cell, a copper target (CuK α, λ 0.154nm) was used as the excitation source, the operating voltage was 45KV, the operating current was 40mA, the scanning step size was 0.013 °, the scanning rate was 0.18sec/step, and the scanning time per step was 17.85 s.
The field emission Scanning Electron Microscope (SEM) image was observed using an S-4800 FESEM (manufactured by Hitachi, Japan) with an acceleration voltage of 10KV and an operating current of 7 μ A.
H2S selective catalytic oxidation activity test: the magnesium aluminate spinel prepared in the embodiment, the alumina prepared in the comparative example and the industrial light magnesium oxide are crushed and sieved into particles of 40-60 meshes for H2Evaluation of selective catalytic oxidation activity of S. The test conditions were as follows: the loading of the catalyst was 0.1g, the feed gas was 5000ppm H2S、2500ppm O2And balance gas nitrogen, the flow rate of the raw material gas is 30 mL/min–1The space velocity (WHSV) of the raw material gas is 18000mL g–1·h–1The reaction temperature is 90-270 ℃, and the raw material gas is three-component gas (5000ppm, 2500ppm, N)2Balance gas).
The catalysts prepared in the examples and comparative examples provided by the invention are applied to H2S selective catalytic oxidation of H2The S conversion, sulfur selectivity and sulfur yield calculation formulas are as follows:
sulfur yield ═ H2Conversion of S]X [ Sulfur Selectivity]
And (4) testing the oxidation activity of COS: magnesium aluminate spinel prepared in the above examples and K used in comparative examples2CO3/γ-Al2O3And crushing and sieving industrial light MgO into 40-60 mesh particles for evaluating the oxidation activity of COS. The test conditions were as follows: the loading of the catalyst is 0.1g, and the feed gas is 110mg/m3COS、55mg/m3O2And balance gas nitrogen, the flow rate of the raw material gas is 40 mL/min–1The space velocity (WHSV) of the raw material gas is 24000mL g–1·h–1The reaction temperature is 50-170 ℃, and the catalyst is aerated for 4 hours at normal temperature before reaction.
The catalysts prepared in the examples and comparative examples provided by the present invention are applied to the oxidation reaction of COS, and the calculation formula of the conversion rate of COS is as follows:
FIG. 1 shows X-ray powder diffraction patterns of magnesium aluminate spinels and aluminas prepared in examples 1-3 of the present invention and comparative example 1. As can be seen from the figure, the magnesium aluminate spinel samples all have seven diffraction peaks at the positions of 19.1, 31.2, 36.8, 44.8, 55.6, 59.3 and 65.2 degrees, which are respectively assigned to MgAl2O4Seven crystal planes of (111), (220), (311), (400), (422), (511) and (440) of (JCPDS 77-0435). From the XRD patterns, the prepared 3 samples of magnesium aluminate spinel showed different peak intensities and full widths at half maximum (FWHM), indicating that the grain sizes and crystallinities of the different samples were different. Among them, the characteristic diffraction peak of the magnesium aluminate spinel with the magnesium aluminate molar ratio of 1:2 is sharpest, which indicates that the sample has the best crystallinity. As can be seen from the XRD pattern of comparative example 1, when no Mg source was added to the raw material, alumina was formed.
Fig. 2 is SEM images of a precursor (a) and a calcined (B) of the magnesium aluminate spinel catalyst B prepared in example 2 of the present invention. As shown, the precursor forms a sheet-like structure. After high-temperature roasting, the organic components in the precursorAnd NO3–The radicals forming COxAnd NOxThe gas is discharged to form a mesoporous structure.
FIG. 3 shows the application of the magnesium aluminate spinel catalysts with different magnesium-aluminum ratios prepared in examples 1-3 of the invention and comparative examples 1 and 2 in H2H in the S selective catalytic oxidation reaction at the temperature range of 90 ℃ to 270 DEG C2S conversion profile. As shown in FIG. 2, when the temperature is lower than 210 deg.C, H is gradually increased as the reaction temperature is gradually increased2The conversion of S gradually increased. The magnesium aluminate spinels of examples 1, 2 and 3 prepared by the invention were paired with H when the temperature reached 210 deg.C2The conversion of S reached 100%, whereas the conversions of the magnesia and alumina prepared in comparative examples 1 and 2 were significantly lower than the magnesia alumina spinel catalysts of the examples.
FIG. 4 shows the application of the magnesium aluminate spinel catalysts with different magnesium/aluminum ratios prepared in examples 1-3 of the invention and comparative examples 1 and 2 in H at 90-270 ℃2Sulfur selectivity in S selective oxidation reactions. As can be seen from the figure, SO is present at temperatures 180 ℃ above the dew point temperature of sulfur2The sulfur selectivity begins to decrease, and the sulfur selectivity increases with the decrease of the magnesium-aluminum ratio, but the sulfur selectivity of the catalysts prepared in examples 1-3 is not very different and is more than 95%.
FIG. 5 shows the application of the magnesium aluminate spinel catalysts with different magnesium/aluminum ratios prepared in examples 1-3 of the invention and comparative examples 1 and 2 in H at 90-270 ℃2Plot of elemental sulfur yield in S selective oxidation reactions. As can be seen from the figure, when the temperature is lower than 180 ℃, the elemental sulfur yield curve of the magnesium aluminate spinel catalyst with different magnesium aluminum ratios is connected with H2The S conversion curves were the same. When the temperature is higher than 180 ℃, the temperature is reduced to be higher than 90 percent.
FIG. 6 shows the H at 210 ℃ of the magnesium aluminate spinel catalyst prepared in example 2 of the invention2Graph of S selective oxidation reaction stability. As can be seen from the figure, H is within 43 hours of the reaction2The conversion rate of S is always stabilized above 98%, and the selectivity of elemental sulfur is stabilized above 95%.
FIGS. 7 and 8 are graphs of Mg/Al prepared in examples 1 to 3 of the present invention at different Mg/Al ratiosSpinel catalyst and comparative examples 2 and 3 COS conversion and H applied to COS oxidation activity test at 50 to 170 c2S concentration profile. From the COS conversion rate graph, it can be seen that the magnesium aluminate spinel catalysts prepared in examples 1 to 3 can maintain 100% of the COS conversion rate at 130 ℃, and the COS conversion rate slightly decreases as the temperature continues to increase. From H2As can be seen in the S concentration graph, the catalysts prepared in examples 1-3 produced H compared to comparative examples 2 and 32S is always maintained at a low concentration, wherein H of the catalysts A and B is increased in temperature2The S concentration is maintained at 5mg/m3Indicating that COS is almost completely oxidized to elemental sulfur in one step.
FIGS. 9 and 10 show the magnesia alumina spinel catalyst prepared in example 2 of the present invention at 70 deg.C and a feed gas space velocity (WHSV) of 12000mL g–1·h–1The following graph is applied to the COS oxidation stability test. As can be seen from the figure, the conversion rate of COS is maintained at 100% in the first 25H of the reaction, the COS begins to slowly decline in 25-30H, and the rate of decline is accelerated when the COS exceeds 30H, while H is2The S concentration is always maintained at 3mg/m3Hereinafter, it is shown that COS is almost completely oxidized to elemental sulfur in one step.
In conclusion, the magnesium aluminate spinels with different magnesium-aluminum ratios prepared by the invention are H2The S selective catalytic oxidation reaction and the COS oxidation reaction both have good catalytic performance and good chemical stability, and the magnalium spinel type catalyst has great application potential in the field of oxidative desulfurization.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the magnesium aluminate spinel catalyst is characterized in that soluble magnesium salt and soluble aluminum salt are used as raw materials, an organic solvent is used as an oxygen donor and a solvent, and the catalyst is prepared by a hydrothermal method, wherein the mass ratio of the soluble magnesium salt to the soluble aluminum salt is 2: 1-1: 4.
2. The method of claim 1, wherein the soluble magnesium salt is MgCl2、Mg(NO3)2、MgSO4One or more of them.
3. The method for preparing the magnesium aluminate spinel catalyst according to claim 1, wherein the soluble aluminum salt is one or more of aluminum tert-butoxide, aluminum isopropoxide and aluminum triethoxide.
4. The method for preparing the magnesium aluminate spinel catalyst according to claim 1, wherein the organic solvent is one or more of absolute ethyl alcohol, absolute isopropyl alcohol and absolute isopropyl ether.
5. The preparation method of the magnesium aluminate spinel catalyst according to claim 1, which is characterized by comprising the following steps:
a, weighing soluble magnesium salt and soluble aluminum salt according to a proportion, adding the soluble magnesium salt and the soluble aluminum salt into an organic solvent, and stirring the obtained mixed solution at room temperature for 2-24 hours;
b, transferring the mixed solution prepared in the step A into a hydrothermal kettle, and carrying out hydrothermal treatment at 130-180 ℃ for 6-18 h;
c, dropwise adding an acid solution into the product prepared in the step B, adjusting the pH value to 4-6, and magnetically stirring for 0.5-2 hours;
d, centrifuging and drying the product prepared in the step C to obtain a magnesium aluminate spinel precursor;
and E, roasting the precursor prepared in the step D at the temperature of 600-900 ℃ to obtain the magnesium aluminate spinel catalyst.
6. Preparation of magnesium aluminate spinel catalyst according to claim 5The preparation method is characterized in that in the step A, the volume of the organic solvent is 50-80 mL; in the step C, the acid solution is HCl or HNO3、H2SO4The concentration of one or more of the (B) is 0.5-1.5 mol/L, and the dropping amount is 5-10 mL.
7. The preparation method of the magnesium aluminate spinel catalyst according to claim 5, wherein in the step D, the drying temperature is 60-120 ℃, and the drying time is 6-18 h.
8. The preparation method of the magnesium aluminate spinel catalyst according to claim 5, wherein in the step E, the roasting time is 6-18 h, and the temperature rise rate in the roasting process is 4-6 ℃/min.
9. Use of a magnesium aluminate spinel catalyst prepared by a process according to any of claims 1 to 8, wherein the catalyst is for use in H2S selective oxidation reaction, wherein the reaction temperature is 90-270 ℃, the pressure is normal pressure, and the volume space velocity is 12000-18000 h–1。
10. The application of the magnesia alumina spinel catalyst prepared by any one of the methods of claims 1 to 8, wherein the catalyst is used for oxidation reaction of COS, the reaction temperature is 30 ℃ to 170 ℃, the pressure is normal pressure, and the volume space velocity is 12000 to 24000h–1。
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