CN110898823B - 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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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 52
- 239000011029 spinel Substances 0.000 title claims abstract description 52
- 239000011777 magnesium Substances 0.000 title claims abstract description 47
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 41
- -1 Magnesium aluminate Chemical class 0.000 title claims abstract description 40
- 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 38
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 17
- 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 14
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000003960 organic solvent 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 10
- 159000000003 magnesium salts Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-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
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 26
- 239000007789 gas Substances 0.000 abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 abstract description 17
- 239000011593 sulfur Substances 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 15
- 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 20
- 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
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 229910003023 Mg-Al Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 235000019441 ethanol Nutrition 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-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
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052566 spinel group Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination 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
- 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
- 238000005259 measurement 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
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005855 radiation Effects 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
- 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
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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- 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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- B01J35/00—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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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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, 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 applies the magnesium aluminate spinel to hydrogen sulfide (H) for the first time 2 S) selective oxidation field and carbonyl sulfide (COS) oxidation field. At a lower reaction temperature, the prepared magnesia-alumina spinel catalyst is used in H 2 Higher H in S selective oxidation reaction 2 S 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 H 2 A 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 generated 2 S is mainly used) and organic sulfur gas (mainly COS), the emission of sulfur-containing gas not only seriously pollutes the environment, but alsoCan cause 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 H 2 S is not completely removed. To address this problem, one can selectively oxidize H at 100% of theoretical 2 The technology of S into elemental sulfur becomes a hotspot of research. The reaction equation involved therein is as follows (equation 1 is the main reaction, equations 2 and 3 are side reactions):
H 2 s 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 H 2 The selective oxidation of S into elemental sulfur has good application prospect. Alumina (Al) 2 O 3 ) Rich resources, stability, no toxicity, rich acid sites on the surface, in H 2 The field of S selective oxidation has made a certain progress. But their catalytic activity is often unsatisfactory. Iron oxide (Fe) 2 O 3 ) Has higher oxidation activity and is H with the widest industrial application 2 S selective oxidation catalysts, but have low sulfur selectivity due to the excess oxygen required. Therefore, the development of a high-efficiency and high-selectivity catalyst is a key 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 reaction 2 S gas, and then removing generated H through a desulfurizing agent 2 And S. This requires a series of process combinations due to the need for subsequent H removal 2 S, the equipment investment and the operation cost are relatively high. In addition, the process has high water consumption and high sewage discharge capacity, and further application in the coal chemical industry is limited. 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 Al 2 O 3 The 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 potential 2 S 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
Aiming at the defects of the prior art, the invention provides a novel preparation method of magnesium aluminate spinel and application thereof in the field of desulfurization, and solves the problem of H in the prior art 2 The S selective oxidation catalyst has the problems of low activity, poor selectivity and stability and the like, and simultaneously solves the defects of complex 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 time 2 And the 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 MgCl 2 、Mg(NO 3 ) 2 、MgSO 4 One 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 h.
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 HNO 3 、H 2 SO 4 The 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 H 2 S 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, theThe 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 H 2 The catalyst has good activity in S selective oxidation reaction and COS oxidation reaction, not only greatly widens the application range of the magnesium-aluminum spinel material, but also provides a new idea 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 m 2 The 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-aluminum 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 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 invention 2 H in S selective catalytic oxidation 2 (iv) 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 invention 2 S selective catalytic oxidation reaction sulfur selectivity curve diagram;
FIG. 5 shows an embodiment of the present inventionCatalysts A-E in examples 1-3 and comparative examples 1, 2 are in H 2 S selective catalytic oxidation reaction sulfur simple substance yield curve chart;
FIG. 6 shows catalyst B prepared in example 2 of the present invention, test H 2 S is a graph of the stability of the selective catalytic oxidation reaction;
fig. 7 is a graph showing a COS conversion rate in a COS oxidation reaction process of catalysts in examples 1 to 3 and comparative examples 2 and 3 of the present invention;
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 invention 2 S 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 invention 2 S 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 by magnetic stirring at room temperature for 15h, transferring the solution into a 100mL high-pressure reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 12h, then naturally cooling at room temperature, cooling, adding 5mL of 1mol/L dilute nitric acid, 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 Mg-Al spinel, wherein the mark is Mg-Al 1 Al 1 O, namely the catalyst A.
Example 2
Weighing 5.106g of aluminum isopropoxide, 3.205g of magnesium nitrate and 75mL of ethanol, mixing the mixture with the ethanol at room temperature for 12 hours by magnetic stirring, transferring the solution into a 100mL high-pressure reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 12 hours, naturally cooling the solution at room temperature, adding 5mL of 1mol/L dilute nitric acid after cooling, carrying out magnetic stirring for 2 hours, centrifuging, and precipitating the precipitate at 10Drying at 0 deg.C for 12h, and calcining at 750 deg.C for 12h to obtain final product magnesium aluminate spinel (labeled as Mg) 1 Al 2 O, 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 Mg 1 Al 3 O, 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 K 2 CO 3 /γ-Al 2 O 3 Labeled as F.
And (3) characterization and analysis:
x-ray powder diffraction (XRD) measurements were carried out using an X' pertpro powder diffractometer from Panalytical to determine the phase composition of the catalyst. The detector is an X' cell, a copper target (CuK α, λ ═ 0.154nm) is used as an excitation radiation source, the operating voltage is 45KV, the operating current is 40mA, the scanning step size is 0.013 °, the scanning rate is 0.18sec/step, and the scanning time per step is 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.
H 2 S selectionSexual 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 H 2 Evaluation 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 H 2 S、2500ppm O 2 And balance gas nitrogen, the flow rate of the raw material gas is 30 mL/min –1 The space velocity (WHSV) of the raw material gas is 18000mL g –1 ·h –1 The reaction temperature is 90-270 ℃, and the raw material gas is three-component gas (5000ppm, 2500ppm, N) 2 Balance gas).
The catalysts prepared in the examples and comparative examples provided by the invention are applied to H 2 S selective catalytic oxidation of H 2 The S conversion, sulfur selectivity and sulfur yield calculation formulas are as follows:
sulfur yield ═ H 2 Conversion 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 examples 2 CO 3 /γ-Al 2 O 3 And 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/m 3 COS、55mg/m 3 O 2 And balance gas nitrogen, the flow rate of the raw material gas is 40 mL/min –1 The space velocity (WHSV) of the raw material gas is 24000mL g –1 ·h –1 The reaction temperature is 50-170 ℃, and the catalyst is ventilated for 4 hours at normal temperature before reaction.
The catalysts prepared in the examples and the comparative examples provided by the invention are applied to the oxidation reaction of COS, and the calculation formula of the conversion rate of COS is as follows:
FIG. 1 is an X-ray powder diffraction pattern of magnesia-alumina spinel and alumina prepared in examples 1-3 of the present invention and comparative example 1. As can be seen from the figure, the magnesia-alumina spinel samples all have seven diffraction peaks at 19.1, 31.2, 36.8, 44.8, 55.6, 59.3 and 65.2 degrees, which are respectively assigned to MgAl 2 O 4 Seven 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 and NO in the precursor 3– The radicals forming CO x And NO x The 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 H 2 H in the S selective catalytic oxidation reaction at the temperature range of 90 ℃ to 270 DEG C 2 S conversion plot. As shown in FIG. 2, when the temperature is lower than 210 deg.C, H is gradually increased as the reaction temperature is gradually increased 2 The 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.C 2 The conversion rate of S reached 100%, whereas the conversion rates of the magnesia and alumina prepared in comparative examples 1 and 2 were significantly lower than those of the magnesia-alumina spinel catalysts of the examples.
FIG. 4 shows Mg-Al spinel catalysts and pairs prepared in examples 1-3 of the present invention with different Mg-Al ratiosRatios 1, 2 applied to H at 90 deg.C to 270 deg.C 2 Sulfur 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 sulfur 2 The sulfur selectivity begins to decrease, and the sulfur selectivity increases with the decrease of the Mg/Al ratio, but the sulfur selectivity of the catalysts prepared in examples 1-3 is not much different and is larger 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 ℃ 2 Plot 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 H 2 The 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 ℃ for the Mg-Al spinel catalyst prepared in example 2 of the present invention 2 S-selective oxidation reaction stability. As can be seen from the figure, H is present within 43 hours of the reaction 2 The S conversion rate is always stabilized above 98%, and the elemental sulfur selectivity is stabilized above 95%.
FIGS. 7 and 8 show COS conversion rates and H ratios of magnesium aluminate spinel catalysts with different magnesium-aluminum ratios prepared in examples 1 to 3 of the invention and COS conversion rates and H ratios of comparative examples 2 and 3 applied to COS oxidation activity tests at 50 ℃ to 170 DEG C 2 S 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 H 2 As can be seen in the S concentration graph, the catalysts prepared in examples 1-3 produced H compared to comparative examples 2 and 3 2 S is always maintained at a low concentration, wherein H of the catalysts A and B is increased in temperature 2 The S concentration is maintained at 5mg/m 3 Indicating 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 –1 Applied to COS oxidation stability testGraph is shown. 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 is 2 The S concentration is always maintained at 3mg/m 3 Hereinafter, 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 H 2 The 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 (6)
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; the soluble magnesium salt is MgCl 2 、Mg(NO 3 ) 2 、MgSO 4 One or more of the above; the soluble aluminum salt is one or more of tert-butyl alcohol aluminum, aluminum isopropoxide and aluminum triethoxide; the organic solvent is one or more of absolute ethyl alcohol, absolute isopropanol and absolute isopropyl ether; the method specifically comprises 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.
2. The preparation method of the magnesium aluminate spinel catalyst according to claim 1, wherein in the step A, the volume of the organic solvent is 50-80 mL; in the step C, the acid solution is HCl or HNO 3 、H 2 SO 4 The concentration of one or more of the (B) is 0.5-1.5 mol/L, and the dropping amount is 5-10 mL.
3. The preparation method of the magnesium aluminate spinel catalyst according to claim 1, wherein in the step D, the drying temperature is 60-120 ℃, and the drying time is 6-18 h.
4. The preparation method of the magnesium aluminate spinel catalyst according to claim 1, 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.
5. Use of a magnesium aluminate spinel catalyst prepared by a process according to any of claims 1 to 4, wherein the catalyst is used for H 2 S 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 。
6. The application of the magnesia alumina spinel catalyst prepared by any one of the methods of claims 1 to 4, wherein 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 。
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| CN108246298A (en) * | 2018-02-12 | 2018-07-06 | 东北石油大学 | A kind of method of nano lamellar solid base removing carbonyl sulfur |
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| CN106824193A (en) * | 2017-01-17 | 2017-06-13 | 福州大学化肥催化剂国家工程研究中心 | A kind of organic sulfur hydrolyst and preparation method thereof |
| CN108325523A (en) * | 2018-02-02 | 2018-07-27 | 华东理工大学 | A kind of propane dehydrogenation catalyst and preparation method thereof |
| CN108246298A (en) * | 2018-02-12 | 2018-07-06 | 东北石油大学 | A kind of method of nano lamellar solid base removing carbonyl sulfur |
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