CN114749196A - Core-shell microwave catalyst, preparation method and application thereof - Google Patents
Core-shell microwave catalyst, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 134
- 239000011258 core-shell material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 69
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910003178 Mo2C Inorganic materials 0.000 claims abstract description 38
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 38
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 7
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910003182 MoCx Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- 238000006555 catalytic reaction Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- -1 polyoxyethylene lauryl ether Polymers 0.000 claims description 5
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- FGQRHNWAVSBJHZ-UHFFFAOYSA-N CCCC[Zr] Chemical compound CCCC[Zr] FGQRHNWAVSBJHZ-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002245 particle Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000010744 Boudouard reaction Methods 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- WPMWEFXCIYCJSA-UHFFFAOYSA-N Tetraethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCO WPMWEFXCIYCJSA-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical group [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; 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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- 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
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
- C01B17/0434—Catalyst compositions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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Abstract
The invention provides a core-shell microwave catalyst, which comprises MoCxCore structure and coated ZrO2A shell structure, the catalyst is MoC-Mo2C@ZrO2A catalyst. The invention also provides a preparation method of the catalyst, which comprises the steps of preparing carbon-containing molybdenum dioxide, carrying out hydrolysis and polycondensation reaction on the carbon-containing molybdenum dioxide, water and zirconium n-butoxide, and drying and roasting the obtained solid to obtain the catalyst. The invention provides a catalyst with a brand-new structure, which has low cost and good wave-absorbing performance(ii) a The preparation method has the advantages of mild preparation conditions, short preparation period, short and safe operation steps, and can realize efficient and direct decomposition of the hydrogen sulfide at a lower reaction temperature.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a core-shell microwave catalyst, and a preparation method and application thereof.
Background
Hydrogen sulfide (H)2S) is a pollutant gas harmful to human health and environment, and is mainly derived from chemical industry (in large quantities, except for relatively small amount of natural sources >4×107t annually). In the future, with the increase of heavy oil refining, H2The production of S is expected to increase further and must be removed or reduced to acceptable levels. On the other hand, from the viewpoint of sustainable energy production, H2S is considered a good resource due to its special elemental composition. Therefore, it is sought to efficiently process H2The process of S and converting it into high value products is of great importance.
At present, the Claus process is often used industrially for treating H2S waste gas, but the process inevitably has SOxThe formation of by-products can lead to further environmental problems. More importantly, the method recovers the sulfur resource (S), but uses valuable hydrogen (H)2) Conversion to low value added water (H)2S+1/2O2→S+H2O)。H2Not only is an indispensable chemical raw material but also is an excellent clean energy source with high energy density (120-142 MJ/kg). However, the natural abundance of hydrogen on earth is almost negligible. If it can generate H2H required by petroleum refining is further obtained from the S waste gas2Then, H generated in the oil and gas industry is solved2S waste gas pollution problem and realizes H2The high-valued conversion of S resources can also reduce the consumption of fossil resources and CO brought by the traditional reforming hydrogen production 2And (4) discharge problems.
Development of direct decomposition H2S is a new technology for producing hydrogen and sulfur to replace the Claus method, which can process H2S waste gas and H can be recovered2The method has great social, economic and ecological benefits. However, H2The direct decomposition reaction of S presents two major challenges. Thermodynamically, H2The S direct decomposition reaction is limited by thermodynamic equilibrium, even at temperatures up to 1000 ℃ H2The conversion of S is also very low (only 30% at 1130 ℃). H2The direct decomposition reaction kinetics of S is slow, and the apparent activation energy is up to 495.62 kJ/mol. Thus, one suitable catalyst and one direct and efficient decomposition process was found to be H2The key of S direct decomposition.
In recent years, microwave-induced catalysis has become more and more widely used in synthetic chemistry. Under the microwave irradiation, the reaction rate can be remarkably accelerated, and the reaction selectivity can be changed. For example: hunt et al reported that under microwave irradiation, the equilibrium position of the Boudouard reaction was changed, lowering the temperature at which CO is the major product from 643 ℃ for the conventional thermal reaction to 213 ℃ for the microwave reaction. Edwards et al activate iron based catalysts (FeAlO) by microwavesx) The method can directly, rapidly and selectively catalyze various plastic raw materials to produce hydrogen and high-value carbon in one step, the reaction time is only 30-90s, the hydrogen yield is as high as 55.6mmol/g, and is 97% of the theoretical yield. Thus, the microwave catalytic reaction mode is more advantageous (MCRM) than the traditional reaction mode (CRM). It follows that it is possible to solve H with microwaves 2Two problems exist in the direct decomposition reaction of S, so that the efficient decomposition of hydrogen sulfide under the low-temperature condition becomes possible.
Previously, decomposition of hydrogen sulfide by microwave dielectric heating by Mingos et al resulted in a conversion of 12% hydrogen sulfide at 800 deg.C, whereas in the conventional reaction mode, the conversion of hydrogen sulfide at 800 deg.C was only 6.5%. Recently, the applicant's topic group has carried out microwave-catalyzed direct decomposition of H2Research on S reaction, finding that CoS-MoS2/γ-Al2O3Microwave catalyst at 788 deg.C, H2The S conversion was 80.33%; the Mo2C @ BN core-shell type microwave catalyst provided in the invention patent CN111203259A directly decomposes H under microwave catalysis corresponding to 650 DEG C2The S conversion rate is as high as 99.9%.
For CoS-MoS2/γ-Al2O3For the microwave catalyst, though H2The conversion rate of S is already obtainedA significant increase, but still not high catalytic activity at low temperatures. For Mo2C @ BN core-shell type microwave catalyst, the microwave catalysis at low temperature directly decomposes H2The catalytic activity of S is good, but the preparation condition of the catalyst is high, which also limits the large-scale application of the catalyst. Therefore, there is still a need in the art for a new low-temperature high-efficiency microwave catalyst and a preparation method thereof.
Disclosure of Invention
The purpose of the invention is realized by the following steps:
The invention firstly provides a core-shell type microwave catalyst, which comprises MoCxCore structure and ZrO coated therewith2A shell structure, the catalyst is MoC-Mo2C@ZrO2A catalyst.
In one embodiment, the ratio of the amount of molybdenum to zirconium in the catalyst is 2 to 20: 1, preferably 3-8: 1.
in the invention, within a certain range, the catalytic activity of the catalyst becomes stronger along with the increase of the content of the zirconium dioxide in the catalyst; however, if the content of zirconium dioxide in the catalyst is too high, the wave-absorbing performance of the catalyst is deteriorated, and the required microwave catalytic effect cannot be achieved.
In a specific embodiment, the catalyst is prepared by preparing carbon-containing molybdenum dioxide, performing hydrolysis and polycondensation reaction on the carbon-containing molybdenum dioxide, water and zirconium n-butoxide, and drying and roasting the obtained solid.
The invention also provides a preparation method of the core-shell microwave catalyst, which comprises the following steps:
step A, preparing powdery carbon-containing molybdenum dioxide;
step B, uniformly mixing the powdery carbon-containing molybdenum dioxide and a dispersing agent, and adding water, a surfactant and n-butyl zirconium to perform hydrolysis and polycondensation reaction; carrying out solid-liquid separation after the reaction, and washing and drying the collected solid to obtain a precursor of the core-shell catalyst; and roasting the precursor at 400-1000 ℃ in a nitrogen atmosphere to obtain the core-shell catalyst, wherein the roasting temperature is preferably 700-900 ℃, and more preferably 700-800 ℃.
In a specific embodiment, the step a comprises uniformly mixing ammonium molybdate and ethylene glycol, adding nitric acid, continuously stirring, performing hydrothermal reaction at 120-180 ℃, washing the generated solid with water and ethanol, drying and roasting at 400-600 ℃ to obtain the powdery carbon-containing molybdenum dioxide, preferably N2And (5) roasting in the atmosphere.
In a specific embodiment, in step B, the dispersant is ethanol, and the surfactant is polyoxyethylene lauryl ether; in the step B, the reaction temperature of hydrolysis and polycondensation of the zirconium n-butyl alcohol is 0-60 ℃, and preferably 20-40 ℃; the solid was washed with ethanol and water in step B.
In a specific embodiment, in the step B, the ratio of the carbon-containing molybdenum dioxide to the dispersant ethanol is 1 g: 50-500 ml, preferably 1 g: 100-200 ml; in the step B, the dosage proportion of the carbon-containing molybdenum dioxide to the water, the polyoxyethylene lauryl ether and the n-butyl alcohol zirconium is 1 g: 0.2-20 ml: 0.2-20 ml: 0.2-15 ml, preferably 1 g: 0.2-1 ml: 0.2-1 ml: 0.5-2 ml; more preferably, the dosage ratio of the carbon-containing molybdenum dioxide to the n-butyl alcohol zirconium in the step B is 1 g: 0.67-1.33 ml, and preferably, the ratio of the carbon-containing molybdenum dioxide to the n-butyl alcohol zirconium in the step B is 1 g: 0.8 to 1.2 ml.
The invention also provides the core-shell microwave catalyst prepared by the method.
The invention also provides a method for directly decomposing H by the catalyst or the catalyst prepared by the method in microwave catalysis2S preparation of H2And sulfur reaction.
In a specific embodiment, MoC-Mo is filled in a quartz reaction tube of a microwave catalytic reaction device2C@ZrO2The catalyst forms a microwave catalytic reaction bed, the mixed gas containing hydrogen sulfide is introduced into the microwave catalytic reaction bed, and microwave and MoC-Mo are added2C@ZrO2Gas-solid reaction under the combined action of catalysts, H2S is directly decomposed into hydrogen and sulfur; the temperature of the microwave catalytic reaction is 300-Selecting 450-650 ℃; and the content of hydrogen sulfide in the mixed gas containing hydrogen sulfide is 1 to 50 vol%, preferably 10 to 20 vol%.
In the invention, the core-shell catalyst and the microwave act synergistically to ensure that H is generated2The direct decomposition rate of S is high and the process is simple and easy to implement. The method and the application not only can achieve direct and efficient decomposition of H2S, and hydrogen resources and valuable sulfur can be obtained.
In the invention, the microwave frequency of the microwave is 2.45 GHz; the microwave power of the microwave is 0.01-1400W, preferably 300-1000W.
Compared with the prior art, the invention has the following advantages: the invention provides a catalyst MoC-Mo with a brand-new structure2C@ZrO2The catalyst has low cost and good wave-absorbing performance; the preparation method has the advantages of mild preparation conditions, short preparation period, short and safe operation steps, and can realize efficient and direct decomposition of the hydrogen sulfide at a lower reaction temperature. Specifically, the method comprises the following steps:
1、MoC-Mo2C@ZrO2the catalyst can efficiently decompose H under the microwave catalysis mode2S, when the reaction temperature is 650 ℃, H2The conversion rate of S can reach 99.9%; the catalyst has good wave-absorbing performance.
2. Mo as provided in the previous application of the applicant2Compared with the C @ BN microwave catalyst, the preparation condition of the catalyst is milder. Prior art Mo2BN in the C @ BN catalyst needs to be formed under the atmosphere of ammonia gas at the temperature of 1000 ℃, while ZrO2 in the catalyst can form a stable structure under the atmosphere of nitrogen gas below 800 ℃; compared with the two methods, the preparation temperature of the catalyst is obviously lower, and the nitrogen atmosphere is more environment-friendly than the ammonia atmosphere. Furthermore, compared with Mo in the prior art2Compared with the C @ BN microwave catalyst, the preparation period of the catalyst is shorter, the operation steps are simpler and safer, and the cost of the catalyst is lower.
Drawings
FIG. 1 shows the core-shell type catalyst MoC-Mo in example 12C@ZrO2(3)、MoC-Mo2C@ZrO2(2) And the non-core-shell MoC catalyst in comparative example 1XRD pattern of (a).
FIG. 2 shows MoC-Mo in example 12C@ZrO2(2) TEM image of catalyst.
FIG. 3 shows MoC-Mo in example 12C@ZrO2(2) EDS elemental map of the middle portion of the catalyst particle.
FIG. 4 shows MoC-Mo in example 12C@ZrO2(3) TEM image of catalyst.
FIG. 5 shows MoC-Mo in example 12C@ZrO2(3) EDS elemental map of the middle portion of the particles of the catalyst.
FIG. 6 shows MoC-Mo in example 12C@ZrO2(3) EDS elemental map of the edge portion of the particles of the catalyst.
Detailed Description
The present invention is described in detail below by way of examples, but the scope of the claims of the present invention is not limited to these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, and do not mean that the conditions must be met for achieving the purpose.
Example 1
In the first step, 6g of ammonium molybdate tetrahydrate is weighed and added into 300mL of ethylene glycol to be stirred for 30 min. Then, 36mL of HNO was added with vigorous stirring3Stirring was continued for 30 min. The mixed solution was then transferred to a 500mL autoclave. The reaction is kept at 160 ℃ for hydrothermal for 14-24 h;
step two, naturally cooling the reaction kettle in the step one, then carrying out suction filtration, washing the reaction kettle for a plurality of times by using distilled water and absolute ethyl alcohol, and carrying out overnight drying in a vacuum drying oven at the temperature of 100 ℃;
Thirdly, putting the sample dried in the second step into a magnetic boat, putting the magnetic boat into a tube furnace, and then introducing N2And roasting at 500 ℃ for 5 hours. After this step, carbon-containing MoO is obtained2And (3) powder.
Fourthly, 3g of the carbon-containing MoO calcined in the third step is weighed2The powder sample was dispersed in 400mL ethanol, sonicated, and then 1mL H was added dropwise with mechanical stirring2O and 1mL of polyoxyethylene lauryl ether (Brij 30), stirring for 30min, respectively adding 2mL and 3mL of n-butyl zirconium dropwise, stirring at 30 deg.C for 8h, centrifuging, and collectingCollected and dried in a drying oven at 80 ℃. Catalyst precursors with different zirconium contents are obtained.
Fifthly, putting the sample dried in the fourth step into a magnetic boat, putting the magnetic boat into a tube furnace, and introducing N2And the sample was calcined at 800 ℃ for 3 hours. The catalysts are respectively named as MoC-Mo2C@ZrO2(2) And MoC-Mo2C@ZrO2(3) Wherein the number in parentheses in the suffix represents the amount of zirconium n-butoxide added dropwise (unit: mL). MoC-Mo is obtained after the step2C@ZrO2A core-shell catalyst powder.
FIG. 1 shows the core-shell type catalyst MoC-Mo in example 12C@ZrO2(3)、MoC-Mo2C@ZrO2(2) And the subsequent XRD patterns of the non-core-shell MoC catalyst of comparative example 1. Wherein three spectral lines from bottom to top respectively represent MoC-Mo2C@ZrO2(3)、MoC-Mo2C@ZrO2(2) And XRD lines for non-core-shell mocs. From the XRD pattern, the MoC sample has broad peaks at 35.0 °, 36.8 °, 39.3 °, 42.6 °, 61.5 ° and 73.9 ° corresponding to the (101), (006), (103), (104), (110) and (116) crystal planes of MoC (JCPDS Card No.08-0384), respectively. MoC-Mo 2C@ZrO2(2) And MoC-Mo2C@ZrO2(3) The catalysts were identified as MoC (JCPDS Card No.08-0384), Mo2C (JCPDS Card No.35-0787) and ZrO2(JCPDS Card No. 49-1642). Wherein MoC-Mo2C @ ZrO2(3) Medium ZrO2Diffraction peak ratio of (3) MoC-Mo2C@ZrO2(2) The diffraction peak is sharper and stronger, has higher crystallization property, and indirectly verifies the MoC-Mo2C@ZrO2(3) ZrO of (1)2The content is higher. Furthermore, MoC-Mo2C@ZrO2(3) Medium MoC and Mo2Diffraction peak ratio of C MoC-Mo2C@ZrO2(2) The diffraction peak of (a) is relatively weak.
FIGS. 2 and 3 are the MoC-Mo diagrams of example 1, respectively2C@ZrO2(2) TEM image and MoC-Mo of catalyst2C@ZrO2(2) EDS elemental map of the middle portion of the catalyst particle. FIG. 4, FIG. 5 and FIG. 6 are the respective views of MoC-Mo in example 12C@ZrO2(3) TEM image of catalyst, MoC-Mo2C@ZrO2(3) EDS elemental map of the middle and edge portions of the catalyst particles. As can be seen from FIG. 2, MoC-Mo2C@ZrO2(2) The lattice spacing of the sample particles was 0.23nm and 0.24nm, corresponding to the (101) and (006) crystal planes of Mo2C, respectively, and the formation of the lattice was observed outside the particles (as shown in the upper right inset of fig. 2). But in MoC-Mo2C@ZrO2(2) ZrO not being clearly visible on the particles2While the atomic ratio of the Zr element to the Mo element was 0.01 as can be seen from the middle portion of the EDS sample particle of fig. 3, the result indicates MoC — Mo 2C@ZrO2(2) The Zr content in the middle part of the particles was low.
However, unlike MoC-Mo2C@ZrO2(2) That is, MoC-Mo shown in FIG. 42C@ZrO2(3) A clear assignment to ZrO was observed on the sample particles2Of (111) and (220), whether the edge (lower right in FIG. 4) or the middle part (lower left in FIG. 4) of the grain, and ZrO2The lattice spacings of the (111) and (220) crystal planes of (2) are 0.29nm and 0.18nm, respectively. In addition, FIG. 4 shows the lattice spacings at 0.23nm and 0.24nm, which are attributed to Mo, respectively2The (101) and (006) crystal planes of C and MoC are consistent with the characterization results of XRD. Likewise, for MoC-Mo2C@ZrO2(3) The sample particles were also subjected to EDS characterization, and FIG. 5 shows that the atomic ratio of Zr element to Mo element in the middle portion of the particles was 0.18, while FIG. 6 shows that the atomic ratio of Zr to Mo in the peripheral portion of the particles was 1.03, indicating that MoC-Mo2C@ZrO2(3) ZrO in catalyst2In MoC-Mo2The surface of the C core is uniformly coated.
Example 2
In a laboratory, the catalyst prepared by the method is used for catalyzing the direct decomposition of hydrogen sulfide, wherein H is used2S Standard gas is N provided by Dalianda Special gas Co Ltd2And H2S in the mixture, wherein H2The S content was 15 vol%.
Detection of H2The gas chromatograph (2) model is Agilent GC 7890A.
Prepared by the method of example 1And a plurality of microwave catalysts are respectively filled in the quartz tube reactor to form a catalyst bed layer, the filling amount is 2g, and the mesh number is 20-60 meshes. Introduction of H2S Standard gas (15 vol% of H is used in the invention)2S and 85 vol% N2The mixed gas of (2) was subjected to an experiment) the flow rate was 60mL/min, and the reaction pressure was normal pressure. Regulating microwave power, changing the reaction bed temperature of the catalyst to maintain the bed temperature at 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C and 650 deg.C, respectively, and performing microwave catalysis to directly decompose H2S experiments, the results are shown in Table 1, Table 1 shows MoC-Mo at different temperatures2C@ZrO2The conversion rate of the catalyst under the action of microwaves.
TABLE 1
From the above table, it is understood that the decomposition rate of hydrogen sulfide increases with an increase in temperature. At the temperature of a catalyst bed layer of 650 ℃, MoC-Mo2C@ZrO2(3) H of catalyst2S conversion rate as high as 99.9%, indicating that H2S is almost completely decomposed. MoC-Mo2C@ZrO2(2) Catalyst bed temperature at 650 ℃ H2The S conversion was 93.1%.
Comparative example 1
In the first step, 6.000g of ammonium molybdate tetrahydrate is weighed into 300mL of ethylene glycol and stirred for 30 min. Then, 36mL of HNO was added with vigorous stirring3Stirring was continued for 30 min. The mixed solution was then transferred to a 500mL autoclave. The reaction is kept at 160 ℃ for hydrothermal for 14-24 h;
Step two, naturally cooling the reaction kettle in the step one, then carrying out suction filtration, washing the reaction kettle for a plurality of times by using distilled water and absolute ethyl alcohol, and carrying out overnight drying in a vacuum drying oven at the temperature of 100 ℃;
thirdly, putting the sample dried in the second step into a magnetic boat, putting the magnetic boat into a tube furnace, and then introducing N2And roasting at 500 ℃ for 5 h. After this step, carbon-containing MoO is obtained2And (3) powder.
Fourthly, putting the sample obtained in the third step into a porcelain boat, and putting the porcelain boat into the porcelain boatThe magnetic boat is put into a tube furnace, and then N is introduced2And roasting at 800 ℃ for 3 h. A non-core-shell MoC powder was obtained.
Comparative example 2
The MoC microwave catalyst prepared in the comparative example 1 is respectively filled in a quartz tube reactor to form a catalyst bed layer, the filling amount is 2g, and the mesh number is 20-60 meshes. Introduction of H2S Standard gas (15 vol% H is used in the invention)2S and 85 vol% N2The mixed gas of (2) was subjected to an experiment) the flow rate was 60mL/min, and the reaction pressure was normal pressure. Regulating microwave power, changing the reaction bed temperature of the catalyst to maintain the bed temperature at 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C and 650 deg.C, respectively, and performing microwave catalysis to directly decompose H2S experiments, the results are shown in Table 2, Table 2 showing partially sulfided Mo at different temperatures2C, the conversion rate of the catalyst under the action of microwaves.
TABLE 2
From the above table, H is within the temperature range of 450-650 deg.C of the catalyst bed2The S conversion increases with increasing bed temperature. The conversion rate at 450 ℃ is 27.0%, the conversion rate at 500 ℃ is 36.8%, the conversion rate at 550 ℃ is 50.6%, the conversion rate at 600 ℃ is 72.7%, and the conversion rate at 650 ℃ is up to 88.2%. While the invention has ZrO2Coated MoC-Mo2C@ZrO2Corresponding to a conversion of up to 99.9% at 650 ℃. It can be seen that the core-shell catalysts of the present invention are useful for H2The conversion of the S decomposition reaction was much higher than the non-core-shell MoC catalyst in comparative example 1.
Comparative example 3
Table 3 shows MoC-Mo at different temperatures2C@ZrO2(3) The conversion rate of the catalyst and the non-core-shell type MoC catalyst provided in comparative example 1 and the non-core-shell type molybdenum-containing catalyst provided in patent CN111203259A under the action of microwaves.
TABLE 3
The invention patent CN111203259A provides a microwave catalyst, and the non-core-shell type molybdenum-containing catalyst prepared by the method disclosed in the invention is H at different reaction temperatures2And (4) S conversion rate. As can be seen from Table 3, H is within the range of 450-650 ℃ as the catalyst bed temperature2The S conversion increases with increasing bed temperature. Its conversion at 650 ℃ corresponds to only 79.5%. In the present invention, there is ZrO 2Coated MoC-Mo2C@ZrO2Corresponding to a conversion of up to 99.9% at 650 ℃. Therefore, the core-shell MoC-Mo provided by the invention2C@ZrO2Catalyst for H2The conversion of the S decomposition reaction was higher than that of the non-core-shell MoC catalyst in comparative example 1 and that of the non-core-shell molybdenum-containing catalyst in CN 111203259A.
Comparative example 4
In the published data of the background art, hydrogen sulfide hardly decomposes at 800 ℃ or lower in the conventional heating reaction mode without adding a catalyst.
Comparative example 5
Table 4 shows the MoC-Mo alloys of the present invention at different temperatures2C@ZrO2(3) Catalyst and catalyst 30% NiS/30% gamma-Al provided in patent CN104437553A2O3/40％BaMn0.2Cu0.8O3Conversion under the action of microwaves.
TABLE 4
The invention patent CN104437553A provides a microwave catalyst, which is a composite catalyst comprising an active component and a cocatalyst component, wherein the active component is nickel sulfide and/or cobalt sulfide, and the cocatalyst component is a perovskite catalyst component; the microwave catalyst also optionally comprises a carrier, and the microwave catalystThe carrier is selected from gamma-Al2O3One or more of active carbon, ZSM-5 molecular sieve and ZSM-11 molecular sieve. 30 percent NiS/30 percent gamma-Al prepared by the method provided by the invention 2O3/40％BaMn0.2Cu0.8O3The catalyst catalyzes the direct decomposition of hydrogen sulfide under the microwave condition to obtain H under different reaction temperatures2Conversion of S. As can be seen from Table 4, under microwave irradiation, MoC-Mo2C@ZrO2Catalyst at different temperatures for H2The conversion rate of S decomposition reaction is higher than 30% NiS/30% gamma-Al2O3/40％BaMn0.2Cu0.8O3A catalyst. Thus, MoC-Mo2C@ZrO2Is a high-efficiency direct decomposition of H2S, a microwave catalyst.
Comparative example 6
Table 5 shows MoC-Mo at different temperatures2C@ZrO2And catalyst Mo provided in prior art invention patent CN111203259A2C @ BN conversion under the action of microwaves was compared.
TABLE 5
The invention patent CN111203259A provides a microwave catalyst, and the core-shell type microwave catalyst comprises Mo2A C core structure and a BN shell structure coated outside. Mo2The C @ BN catalyst catalyzes hydrogen sulfide to be directly decomposed under the microwave condition to obtain H under different reaction temperatures2Conversion of S. As can be seen from Table 5, under microwave irradiation, the MoC-Mo provided in the invention2C@ZrO2The reaction temperature of the core-shell microwave catalyst is 450-600 ℃, and the reaction temperature is H2The conversion rate of S decomposition reaction is higher than that of Mo2C @ BN catalyst and at 650 ℃ and Mo2The conversion of the C @ BN catalyst was consistent. Thus, the MoC-Mo of the invention 2C@ZrO2Core-shell microwave catalyst for microwave catalysis H2The performance of S decomposition reaction is slightly superior to that of Mo2C @ BN catalyst. Due to the fact thatThis, MoC-Mo2C@ZrO2The core-shell type microwave catalyst is a high-effective direct decomposition of H2S, a microwave catalyst. More importantly, compared with the disclosed Mo2C @ BN core-shell microwave catalyst and MoC-Mo provided by the invention2C@ZrO2The preparation condition of the core-shell type microwave catalyst is mild, because Mo2The BN in the C @ BN catalyst is formed at 1000 ℃ under an ammonia atmosphere, and the MoC-Mo of the invention2C@ZrO2The zirconium dioxide in the catalyst only needs to form a stable structure at 800 ℃ and under a nitrogen atmosphere (even lower temperature). Compared with the ammonia gas atmosphere, the nitrogen gas atmosphere is safer and energy-saving and has low cost; the catalyst provided by the invention has the advantages of short preparation period, simple operation steps and the like.
As can be seen from the comparison of the above examples and comparative examples, the present invention provides MoC-Mo2C@ZrO2The conversion rate of the hydrogen sulfide of the catalyst at 600 ℃ can reach 82.7 percent, and the conversion rate of the hydrogen sulfide at 650 ℃ can reach 99.9 percent. The combined action of the catalyst and the microwave can break the decomposition reaction balance of the hydrogen sulfide, greatly improve the conversion rate of the hydrogen sulfide and achieve the aim of efficiently decomposing the hydrogen sulfide at lower reaction temperature.
Although the embodiments of the present invention have been described in detail with reference to the accompanying drawings, the embodiments of the present invention are not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the embodiments of the present invention within the technical idea of the embodiments of the present invention, and these simple modifications all belong to the protection scope of the embodiments of the present invention.
Claims (10)
1. The core-shell microwave catalyst is characterized by comprising MoCxCore structure and ZrO coated therewith2A shell structure, the catalyst is MoC-Mo2C@ZrO2A catalyst.
2. The core-shell microwave catalyst according to claim 1, wherein the ratio of the amount of molybdenum to zirconium in the catalyst is 2-20: 1, preferably 3-8: 1.
3. the core-shell microwave catalyst according to claim 1 or 2, wherein the catalyst is obtained by preparing carbon-containing molybdenum dioxide, subjecting the carbon-containing molybdenum dioxide to hydrolysis and polycondensation with water and zirconium n-butoxide, and drying and calcining the solid obtained by the reaction.
4. A method for preparing the core-shell microwave catalyst according to any one of claims 1 to 3, characterized in that the method comprises the following steps:
Step A, preparing powdery carbon-containing molybdenum dioxide;
step B, uniformly mixing the powdery carbon-containing molybdenum dioxide and a dispersing agent, and then adding water, a surfactant and n-butyl zirconium to perform hydrolysis and polycondensation reaction; carrying out solid-liquid separation after the reaction, and washing and drying the collected solid to obtain a precursor of the core-shell catalyst; and roasting the precursor at 400-1000 ℃ in a nitrogen atmosphere to obtain the core-shell catalyst, wherein the roasting temperature is preferably 700-900 ℃, and more preferably 700-800 ℃.
5. The preparation method according to claim 4, wherein the step A comprises the steps of uniformly mixing ammonium molybdate and ethylene glycol, adding nitric acid, continuously stirring, performing hydrothermal reaction at 120-180 ℃, washing the generated solid with water and ethanol, drying and roasting at 400-600 ℃ to obtain the powdery carbon-containing molybdenum dioxide, preferably N2And (5) roasting in the atmosphere.
6. The method according to claim 4, wherein in step B, the dispersant is ethanol, and the surfactant is polyoxyethylene lauryl ether; in the step B, the reaction temperature of hydrolysis and polycondensation of the zirconium n-butyl alcohol is 0-60 ℃, and preferably 20-40 ℃; the solid was washed with ethanol and water in step B.
7. The preparation method according to claim 6, wherein in the step B, the ratio of the carbon-containing molybdenum dioxide to the dispersant ethanol is 1 g: 50-500 ml, preferably 1 g: 100-200 ml; in the step B, the dosage proportion of the carbon-containing molybdenum dioxide to the water, the polyoxyethylene lauryl ether and the n-butyl alcohol zirconium is 1 g: 0.2-20 ml: 0.2-20 ml: 0.2-15 ml, preferably 1 g: 0.2-1 ml: 0.2-1 ml: 0.5-2 ml; more preferably, the dosage ratio of the carbon-containing molybdenum dioxide to the n-butyl alcohol zirconium in the step B is 1 g: 0.67-1.33 ml, and preferably, the ratio of the carbon-containing molybdenum dioxide to the n-butyl alcohol zirconium in the step B is 1 g: 0.8 to 1.2 ml.
8. A core-shell microwave catalyst prepared by the method of any one of claims 4 to 7.
9. A catalyst according to any one of claims 1 to 3 and 8 or a catalyst prepared by a method according to any one of claims 4 to 7 for direct decomposition of H in microwave catalysis2S preparation of H2And the application in sulfur reaction.
10. Use according to claim 9, characterized in that the quartz reaction tube of the microwave catalytic reaction unit is filled with MoC-Mo2C@ZrO2The catalyst forms a microwave catalytic reaction bed, the mixed gas containing hydrogen sulfide is introduced into the microwave catalytic reaction bed, and microwave and MoC-Mo are carried out 2C@ZrO2Gas-solid reaction under the combined action of catalysts, H2S is directly decomposed into hydrogen and sulfur; the temperature of the microwave catalytic reaction is 300-1000 ℃, preferably 450-650 ℃; and the content of hydrogen sulfide in the hydrogen sulfide-containing mixed gas is 1 to 50 vol%, preferably 10 to 20 vol%.
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