CN114713253B - Method for preparing pure alpha-phase molybdenum carbide catalyst by one-step carbonization, catalyst and application - Google Patents
Method for preparing pure alpha-phase molybdenum carbide catalyst by one-step carbonization, catalyst and application Download PDFInfo
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- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000003763 carbonization Methods 0.000 title claims abstract description 40
- 239000010948 rhodium Substances 0.000 claims abstract description 55
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 24
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 22
- 238000010285 flame spraying Methods 0.000 claims abstract description 14
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 150000003283 rhodium Chemical class 0.000 claims abstract 3
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- 238000011068 loading method Methods 0.000 claims description 10
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- 239000011261 inert gas Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 239000000567 combustion gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 3
- 239000003960 organic solvent Substances 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- YKJSOAKPHMIDLP-UHFFFAOYSA-J 2-ethylhexanoate;molybdenum(4+) Chemical compound [Mo+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O YKJSOAKPHMIDLP-UHFFFAOYSA-J 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 1
- 229940010552 ammonium molybdate Drugs 0.000 claims 1
- 235000018660 ammonium molybdate Nutrition 0.000 claims 1
- 239000011609 ammonium molybdate Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 15
- 238000007598 dipping method Methods 0.000 abstract 1
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- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 19
- 229910002091 carbon monoxide Inorganic materials 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000012495 reaction gas Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
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- 239000013078 crystal Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IMHQFVGHBDXALM-UHFFFAOYSA-N 2,2-diethylhexanoic acid Chemical compound CCCCC(CC)(CC)C(O)=O IMHQFVGHBDXALM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal carbides Chemical class 0.000 description 1
Classifications
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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
- 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
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a method for preparing a pure alpha-phase molybdenum carbide catalyst by one-step carbonization induced by noble metal rhodium and application thereof. The preparation method comprises the following steps: (1) preparing molybdenum trioxide powder by adopting a flame spraying method; (2) Dipping molybdenum trioxide powder into rhodium salt solution, and drying to obtain noble metal-loaded molybdenum trioxide; (3) Carbonizing the sample obtained in the step (2) under the carbon source gas. According to the invention, the molybdenum trioxide nano particles are prepared by using a flame spraying method, the carbonization process of molybdenum trioxide can be obviously changed by using trace noble metal rhodium, and alpha-phase molybdenum carbide with higher purity is obtained by one-step carbonization, so that the high-pollution ammoniation process is omitted. The invention also discloses a rhodium-loaded alpha-phase molybdenum carbide catalyst and application thereof in water vapor shift reaction, and the result shows that the molybdenum carbide catalyst prepared by the method has higher activity and stability.
Description
Technical Field
The invention relates to a molybdenum carbide catalyst which is formed by converting molybdenum oxide into rhodium after loading noble metal rhodium through one-step example 1, a preparation method and application thereof, in particular to a preparation method for preparing a pure alpha-phase molybdenum carbide catalyst through one-step carbonization and application thereof in water vapor shift reaction.
Background
The water vapor shift reaction (WGS) is a reaction commonly used for industrial hydrogen production, and is mainly applied to the industries of hydrogen production and ammonia synthesis by taking coal, petroleum and natural gas as raw materials. Among the catalysts existing in the past, copper-based and iron-based catalysts are mainly used in industry, and the activity is poor. In recent years, transition metal carbides have become an emerging catalytic material system, with molybdenum carbide being an object of interest. The research shows that the alpha-phase molybdenum carbide catalyst shows extremely high activity in the water-gas shift reaction, which is far higher than beta-phase molybdenum carbide. This is because the alpha-phase molybdenum carbide can activate H 2 O-H bond in O molecule also provides new possibility for hydrogen production by water dissociation.
However, alpha-phase molybdenum carbide catalysisPreparation and application of the agent are difficult: (1) Because alpha-phase molybdenum carbide is in a face-centered cubic structure (FCC), the preparation method is mostly prepared by a two-step carbonization method of high-temperature ammoniation, temperature reduction and high-temperature carbonization, the method has complex steps and high cost, high-purity ammonia gas is required to be used for treatment at high temperature in the preparation process, environmental pollution is easily caused, potential safety hazards exist, and the requirement on the corrosion resistance of equipment is high; (2) The alpha-phase molybdenum carbide is useful for dissociating H 2 O has the advantage, but is also very easy to be H-substituted during the reaction 2 O is oxidized into molybdenum oxide, so that the activity is lost, and the poor stability is one of bottleneck problems of the alpha-phase molybdenum carbide catalyst in actual application.
The patent application of Shichuan et al published as 'a pure alpha-phase molybdenum carbide supported noble metal catalyst and a preparation method and application thereof' (patent publication number: CN 104923274A) adopts a one-step carbonization method to synthesize a noble metal gold or platinum or palladium supported pure alpha-phase molybdenum carbide catalyst, and the obtained molybdenum carbide has a crystal form of pure alpha-phase molybdenum carbide as can be seen from an XRD (X-ray diffraction) spectrogram, but the method needs to carry out unbalanced plasma treatment to replace a roasting process before carbonization, and the method can not obtain pure alpha-phase molybdenum carbide through an ammoniation process, but the preparation period of the catalyst is longer and the preparation process is more complicated.
Martin et al published patent application "Pt/alpha-MoC 1-x The supported catalyst and its synthesis and application (patent publication No. CN 104707636A) adopts one-step carbonization method to synthesize noble metal platinum supported alpha-phase molybdenum carbide catalyst, and uses the catalyst in aqueous phase methanol reforming reaction, and from the data and XRD spectrogram, it can be seen that the obtained molybdenum carbide crystal form is pure alpha-phase molybdenum carbide, but in the preparation process of the catalyst, high-temperature roasting treatment is required, and the noble metal Pt content is higher, so that the cost is increased.
The invention provides a method for preparing molybdenum trioxide by adopting a flame spraying method, the whole process does not need high-temperature roasting or other pretreatment procedures, the molybdenum oxide loaded with rhodium can be carbonized in one step to prepare alpha-phase molybdenum carbide, and the alpha-phase molybdenum carbide catalyst with higher purity can be obtained by only needing trace noble metal rhodium. The method not only simplifies the preparation flow of the alpha-phase molybdenum carbide, reduces the ammonia leakage risk and the pollution and equipment corrosion problems, but also obviously improves the activity and stability of the alpha-phase molybdenum carbide in the water-gas shift reaction.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a preparation method for synthesizing pure alpha-phase molybdenum carbide by a one-step carbonization method, which aims to simplify the synthesis method of the alpha-phase molybdenum carbide, omit the high-pollution and high-cost ammoniation process required in the preparation process, reduce the environmental pollution risk and save the production cost.
In order to achieve the above purpose, the present invention adopts the following scheme:
the invention provides a preparation method of noble metal rhodium-induced alpha-phase molybdenum carbide, which comprises the following steps:
(1) Preparing molybdenum trioxide powder by adopting a flame spraying method;
(2) Carrying out impregnation treatment on the molybdenum trioxide powder obtained in the step (1) by using a noble metal salt solution to obtain rhodium-loaded molybdenum trioxide;
(3) Carbonizing the rhodium-loaded molybdenum trioxide obtained in the step (2) for 1-8 hours at 600-800 ℃ under a carbon source gas, wherein CH is contained in the carbon source gas 4 The volume fraction of (2) is 10-30%, the rest is hydrogen, the flow rate of the mixed gas is 20-500ml/min, and the heating rate is 1-10 ℃/min.
The second technical problem to be solved by the invention is to prepare the alpha-phase molybdenum carbide catalyst loaded with the noble metal rhodium by using the preparation method, wherein the mass percentage of Rh is 0.02-5%.
The invention solves the technical problem of providing the application of the alpha-phase molybdenum carbide catalyst loaded with the noble metal rhodium in water vapor shift reaction.
The condition of the alpha-phase molybdenum carbide catalyst loaded with the noble metal rhodium for water vapor shift reaction is as follows, the mass airspeed is 30000-1800000ml/g/H, the volume fraction of CO in the reaction atmosphere is 1-10%, and H 2 The volume fraction of O is 2-20%, and the reaction temperature is 120-350 ℃.
The beneficial effects of the invention are as follows:
(1) The invention adopts the flame spraying method to prepare the trioxygenThe molybdenum carbide particles are smaller and are easier to reduce, thereby being beneficial to reducing the carburization temperature. Meanwhile, by utilizing the characteristic of noble metal rhodium, H in carbonization atmosphere is activated 2 And CH (CH) 4 Greatly reduces the carburization temperature in the carbonization process of molybdenum trioxide. Trace rhodium (0.02-0.1% by mass) can be added to realize one-step carbonization to prepare high-purity alpha-phase molybdenum carbide, and researches show that trace rhodium can promote the carbonization process from molybdenum trioxide to MoO with face-centered cubic structure x C y Intermediate transformation, thereby further carbonizing to form alpha-phase molybdenum carbide, while inhibiting MoO 2 Conversion to beta-Mo 2 C carbonization route. Compared with the prior art, the method has the advantages that the used noble metal amount is low, the purity of the alpha-phase molybdenum carbide is high, the use amount of the noble metal is obviously reduced, the high-pollution and high-energy-consumption ammoniation process required in the original preparation process of the pure alpha-phase molybdenum carbide is omitted, and a novel method is provided for the industrial production of the pure alpha-phase molybdenum carbide.
(2) The catalyst prepared by the method has excellent water vapor transformation performance when only trace noble metal rhodium is added, and experimental results prove that the catalyst has the advantages of high water vapor transformation performance when the catalyst contains 10 percent of CO/20 percent of H 2 In the reaction atmosphere of O/70% He, 0.025% Rh/MoO at a space velocity of 180000ml/g/h 3 alpha-MoC obtained by carbonizing catalyst in one step 1-x At 200℃the reaction rate over the unit catalyst was 112. Mu. Mol CO /(g cat S) far higher than the alpha-MoC prepared by adopting a high-pollution ammonification method 1-x Is 83. Mu. Mol CO /(g cat ·s)。
(3) The catalyst prepared by the method can also obviously improve the stability of alpha-phase molybdenum carbide in the water vapor shift reaction. For example, 2% Rh/alpha-MoC 1-x After the catalyst reacts for 9 hours at 300 ℃, the CO conversion rate still has 70 percent, and the alpha-MoC prepared by an ammonification method 1-x After 7 hours of reaction, the CO conversion rate of the catalyst is reduced to below 5%.
Drawings
FIG. 1 is a 2% Rh/FSP-alpha-MoC obtained in example 1 1-x 1% Rh/FSP-MoC obtained in example 2 x And 0.025% Rh/FSP-MoC obtained in example 3 x With the pure beta obtained in comparative example 1XRD contrast pattern of phase molybdenum carbide and pure alpha phase molybdenum carbide prepared by ammonification method obtained in comparative example 2;
FIG. 2 shows the result of example 1, 2% Rh/FSP-alpha-MoC 1-x 1% Rh/FSP-MoC obtained in example 2 x And 0.025% Rh/FSP-MoC obtained in example 3 x An activity comparison chart of the catalytic water vapor shift reaction of the pure beta-phase molybdenum carbide obtained in the comparative example 1 and the pure alpha-phase molybdenum carbide obtained in the comparative example 2;
FIG. 3 shows the result of example 3, 0.025% Rh/FSP-MoC x (700-2 h carbonization conditions) and 0.025% Rh/FSP-MoC obtained in example 4 x (carbonization conditions of 650-8 h) and 0.025% Rh/FSP-MoC obtained in example 5 x (700-0 h carbonization conditions) and 0.025% Rh/FSP-MoC obtained in example 6 x XRD contrast pattern of the catalyst (600-2 h carbonization conditions);
FIG. 4 shows the result of example 3, 0.025% Rh/FSP-MoC x (700-2 h carbonization conditions) and 0.025% Rh/FSP-MoC obtained in example 4 x (carbonization conditions of 650-8 h) and 0.025% Rh/FSP-MoC obtained in example 5 x (700-0 h carbonization conditions) and 0.025% Rh/FSP-MoC obtained in example 6 x (600-2 h carbonization condition) activity comparison chart of the catalyst catalytic water vapor shift reaction;
FIG. 5 is a 2% Rh/FSP-alpha-MoC obtained in example 1 1-x A stability comparison chart of the water vapor shift reaction catalyzed by pure alpha-phase molybdenum carbide obtained in comparative example 2;
FIG. 6 is a 2% Rh/FSP-alpha-MoC obtained in example 1 1-x XRD contrast pattern after application of pure alpha-phase molybdenum carbide obtained in comparative example 2 to the catalysis of water vapor shift reaction stability;
FIG. 7 is a 2% Rh/FSP-alpha-MoC obtained in example 1 1-x With the pure beta-phase molybdenum carbide obtained in comparative example 1, the pure alpha-phase molybdenum carbide obtained in comparative example 2 and 2% Au/FSP-MoC obtained in comparative example 5 x XRD contrast pattern of the catalyst;
FIG. 8 shows the result of example 3, 0.025% Rh/FSP-MoC x With the pure beta-phase molybdenum carbide obtained in comparative example 1, the pure alpha-phase molybdenum carbide obtained in comparative example 2, and 0.025% Au/FSP-MoC obtained in comparative example 3 x And comparative example 4 resulted in 0.025% Pt/FSP-MoC x XRD contrast pattern of the catalyst;
FIG. 9 is a comparison of XRD spectrum changes during carbonization of the pure beta-phase molybdenum carbide catalyst obtained in comparative example 1;
FIG. 10 shows the result of example 3, 0.025% Rh/FSP-MoC x XRD spectrogram change comparison of the catalyst in the carbonization process;
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Example 1
(1) The molybdenum oxide can be prepared by flame spraying. The specific operation of the flame spraying method is that 34.945g of molybdenum acetylacetonate is dissolved in 100ml of benzyl alcohol, and is stirred for about 1h at room temperature to be uniformly mixed, then 100ml of diethyl hexanoic acid (EHA) is added into the solution, and is stirred for more than about 1h at room temperature to be uniformly mixed as much as possible, so that a mixed precursor solution with the concentration of 0.5mol/L is prepared; the prepared solution was pumped into the flame using a syringe at a rate of 5 ml/min. The flame combustion gas is a mixed gas consisting of methane (0.6L/min) and oxygen (1.9L/min), and the mixed gas is sprayed out from a nozzle with the diameter of 2 mm. The method comprises the steps that a large amount of air (5L/min) is blown into a flame area by adopting a gas distribution plate (comprising a cylindrical container with one end being sealed and the other end being open, the peripheral edge of the gas distribution plate with a gas through hole is connected with the open end of the cylindrical container in a sealing way, an air inlet connected with an air pump or an air compressor is arranged on the cylindrical container, the gas distribution plate faces flame), under the driving of high-speed air flow, combustion products rapidly leave the flame area, and the sum of the radial sectional areas of the gas through holes on the gas distribution plate is 3.5 square centimeters. The catalyst particles obtained by combustion are collected by using glass fiber filter paper. The prepared catalyst is FSP-MoO with the particle size of 10-30nm 3 (FSP stands for flame spraying).
(2) 1ml of RhCl of 0.04g/ml is measured out 3 Adding 1g of MoO obtained in the step (1) into the solution 3 Adding about 1ml of water (or ethanol) into the sample, and fully and uniformly stirring; standing the sample for 6h, evaporating the sample in a water bath at 80 ℃ for 2h to obtain 2% Rh/FSP-MoO 3 A precursor;
(3) The step (2) is carried out2％Rh/MoO 3 Tabletting precursor sample, granulating to obtain 20-40 mesh granules, weighing 0.13g, placing into quartz tube reactor, and introducing into gas flow rate of 150ml/min at 20% CH 4 /H 2 Carbonizing at room temperature to 700 deg.C at 5 deg.C/min at 700 deg.C for 2 hr, and cooling to room temperature to obtain 2% Rh/FSP-alpha-MoC 1-x Catalyst (0)<x<1，α-MoC 1-x Molybdenum carbide representing pure alpha phase, the same applies below);
(4) The water vapor shift reaction is directly carried out in a quartz tube reactor in the carbonization step, the catalyst obtained in the step (2) is directly cut into inert gas from carbonized gas for replacement, and then the inert gas is cut into reaction gas for in-situ water vapor shift reaction. The composition of the reaction gas used for water vapor shift is 5% CO/20% H 2 O/75% He (V/V/V), gas mass space velocity of 30000ml/g/h, and reaction temperature of 120-350 ℃;
(5) As the catalyst activity gradually increases with increasing reaction temperature, peaks around 200 ℃, and then continues to increase in temperature, the catalyst activity decreases and the activity of the catalyst exceeds 90% at 200 ℃;
to compare the activity difference of catalysts with different Rh loadings at this temperature, the activity change of the catalyst was measured by increasing the space velocity at 200℃and changing the CO and H 2 O ratio, and the change in CO conversion was observed. The following operation conditions are specifically required to be respectively carried out,
(1) the method comprises the following steps 200 ℃, the composition of reaction gas: 5% CO/20% H 2 O/75% He (V/V/V), airspeed modulation: 30000-60000-120000-180000 ml/g/h;
(2) the method comprises the following steps 200 ℃, the composition of reaction gas: 10% CO/20% H 2 O/70% He (V/V/V), space velocity: 180000 ml/g/h.
Example 2
The procedure and process conditions of this example were the same as in example 1, with the differences only in the following points: 0.5ml of RhCl of 0.04g/ml is measured out 3 The solution was added to 1g of MoO 3 In the preparation of the Rh/MoC catalyst with the loading mass percentage of 1% x A catalyst.
Example 3
The procedure and process conditions of this example were the same as in example 1, with the differences only in the following points: 0.31ml of RhCl of 1.6mg/ml is measured out 3 The solution was added to 1g of MoO 3 In the preparation of the catalyst, rh/MoC with a loading mass percentage of 0.025% was prepared x A catalyst.
Example 4
The procedure and process conditions of this example were the same as in example 3, with the differences only in the following points: the carbonization process is heated from room temperature to 650 ℃, the heating rate is 5 ℃/min, and the carbonization process is kept at 650 ℃ for 8 hours.
Example 5
The procedure and process conditions of this example were the same as in example 3, with the differences only in the following points: the temperature is raised from room temperature to 700 ℃ at a rate of 5 ℃/min, but not at 700 ℃.
Example 6
The procedure and process conditions of this example were the same as in example 3, with the differences only in the following points: the temperature was raised from room temperature to 600℃at a rate of 5℃per minute, and the temperature was maintained at 600℃for 2 hours.
Comparative example 1
(1) The molybdenum oxide can be prepared by flame spraying. The specific operation of the flame spraying method is the same as that of the step (1) of the embodiment 1;
(2) The MoO obtained in the step (1) is processed 3 Tabletting to obtain 20-40 mesh granule, weighing 1g, placing into quartz tube reactor, and introducing into gas with gas flow rate of 150ml/min at 20% CH 4 /H 2 Carbonizing at room temperature to 700 deg.C at 5 deg.C/min at 700 deg.C for 2 hr, and cooling to room temperature in carbonizing atmosphere to obtain FSP-beta-Mo 2 C catalyst (beta-Mo) 2 C represents pure beta-phase molybdenum carbide);
(3) The water vapor transformation reaction is directly carried out in a quartz tube reactor of the carbonization step, the catalyst obtained in the step (3) is directly cut into inert gas from carbonized gas for replacement, and then the inert gas is cut into reaction gas for in-situ water vapor transformationAnd (3) carrying out a replacement reaction. The composition of the reaction gas used for water vapor shift is 5% CO/20% H 2 O/75% He (V/V/V), gas mass space velocity of 30000ml/g/h, and reaction temperature of 120-350 ℃. In each gas switching process, inert gas N is needed 2 The reactor was purged of gas for about 10min to ensure safety.
Comparative example 2
(1) The molybdenum oxide can be prepared by flame spraying. The specific operation of the flame spraying method is the same as that of the step (1) of the embodiment 1;
(2) The MoO obtained in the step (1) is processed 3 Tabletting, granulating to obtain 20-40 mesh granules, weighing 1g, placing into quartz tube reactor, and adding pure NH with gas flow rate of 150ml/min 3 In the atmosphere of (1), the temperature is raised from room temperature to 700 ℃ at a heating rate of 5 ℃/min, the temperature is kept constant at 700 ℃ for 2 hours, and then NH is carried out 3 Rapidly cooling to room temperature under the atmosphere;
(3) The gas was then switched to 20% CH4/H at a gas flow rate of 150ml/min 2 (V/V), in the carbonization atmosphere, carrying out programmed heating carbonization again, heating from room temperature to 700 ℃, wherein the heating rate is 5 ℃/min, and keeping the temperature at 700 ℃ for 2 hours, and then rapidly cooling to room temperature in the carbonization atmosphere;
(4) Finally, at normal temperature, the gas is switched into 1%O with the gas flow rate of 50ml/min 2 Passivating Ar (V/V) for 12h to obtain FSP-alpha-MoC 1-x A catalyst. In each gas switching process, inert gas N is needed 2 Purging the gas in the reactor for about 10 minutes to ensure safety;
(5) Due to the high requirements of the ammoniation treatment on the carbonization equipment, the ex situ water vapor shift evaluation was used herein. The water vapor shift reaction was directly carried out in an additional quartz tube reactor under sample pretreatment conditions of 20% CH at 50ml/min 4 /H 2 The temperature was programmed from room temperature to 700 c at a heating rate of 5 c/min under an atmosphere and kept constant for 2 hours, followed by rapid cooling to room temperature under the atmosphere. Cutting the carbonized gas into inert gas for replacement, and cutting the carbonized gas into reaction gas for in-situ water vapor shift reaction.
The composition of the reaction gas used for water vapor transformation is 5%CO/20％H 2 O/75% He, gas mass space velocity of 30000ml/g/h, and reaction temperature of 120-350 ℃;
(6) The space velocity adjustment step was the same as that of step (5) of example 1.
Comparative example 3
The procedure and process conditions in this example were the same as in example 1, except that the following points were used: 0.56ml of H of 0.38mg/ml is measured out 2 AuCl 4 The solution was added to 1g of MoO 3 In the preparation of the Au/FSP-MoC with the loading mass percentage of 0.025 percent x A catalyst.
Comparative example 4
The procedure and process conditions in this example were the same as in example 1, except that the following points were used: 0.125ml of 2mg/ml (NH 4 ) 2 PtCl 6 The solution was added to 1g of MoO 3 In the preparation of the Pt/FSP-MoC with the loading mass percentage of 0.025 percent x A catalyst.
Comparative example 5
The procedure and process conditions in this example were the same as in example 1, except that the following points were used: 3.6ml of H9.57 mg/ml was measured out 2 AuCl 4 The solution was added to 1g of MoO 3 In the preparation of the Au/FSP-MoC with the loading mass percentage of 2 percent x A catalyst.
The alpha-phase molybdenum carbide catalyst loaded with the noble metal rhodium has excellent catalytic performance on water vapor shift reaction; the catalytic performance is still better under the conditions of high space velocity and low temperature, and the experimental result proves that the catalyst has high catalytic performance under the conditions of 10 percent CO/20 percent H 2 In a reaction atmosphere of O/70% He, 0.025% Rh/alpha-MoC obtained in example 3 at a space velocity of 180000ml/g/h 1-x The reaction rate of the catalyst at 200 ℃ is 112 mu mol CO /(g cat S), better than beta-Mo 2 MoC of C phase and alpha phase mixed crystal and beta phase mixed crystal x Is a water vapor shift reactive activity of (a). In addition, when the loading of rhodium is more than 1%, the pure alpha-phase molybdenum carbide can be promoted to be generated, the stability of the pure alpha-phase molybdenum carbide in the water vapor shift reaction can be obviously improved, and the oxidation of the molybdenum carbide is inhibited. For example, 2% Rh/alpha-MoC 1-x The catalyst still had 79.6% activity at 350 ℃CWhereas the pure alpha-phase molybdenum carbide catalyst had only 10.2% activity at 350 ℃. In summary, this is an inventive technique that is very promising in the field of pure alpha-phase molybdenum carbide preparation and water vapor shift applications.
TABLE 1 comparison of the reaction Rate of the catalysts prepared according to the invention with those of the catalysts already known in the literature in the case of steam-shift reactions
a 11％CO/26％H 2 O/26％H 2 /7％CO 2 /He；
b 11％CO/21％H 2 O/43％H 2 /6％CO 2 /N 2 ；
c 11％CO/26％H 2 O/26％H 2 /7％CO 2 /30％N 2 ；
d 1 bar CO/NaOH solution；
e 10％CO/20％H 2 O/He 。
Claims (7)
1. The method for preparing the pure alpha-phase molybdenum carbide catalyst by one-step carbonization is characterized by comprising the following steps:
1) Flame spraying method for preparing molybdenum trioxide: dissolving an organic precursor containing molybdenum in an organic solvent to obtain a precursor solution, dispersing the precursor solution into liquid drops, introducing the liquid drops into flame for combustion, and collecting molybdenum trioxide powder formed after combustion;
2) Loading noble metal rhodium: immersing the molybdenum trioxide powder obtained in the step (1) in a salt solution of noble metal rhodium, stirring, standing and evaporating to dryness to obtain rhodium-loaded molybdenum trioxide;
3) One-step carbonization: carbonizing the rhodium-loaded molybdenum trioxide prepared in the step (2) under a carbon source gas;
the impregnation method in the step (2) is equal volume impregnation; the concentration of rhodium salt solution is 1-100mg/mL, and the standing time is 6-24h; evaporating to dryness at 60-200deg.CThe evaporating time is 1-20 hours; rhodium salt solution is RhCl 3 Is an aqueous solution of (a); the mass loading of rhodium in the rhodium-loaded molybdenum trioxide is 0.02-2%;
the combustion gas required by flame combustion in the step (1) is a mixed gas of methane and oxygen, and the flow rates of the methane and the oxygen are 0.1-10L/min; the speed of pumping the precursor solution into the flame is 0.1-20mL/min;
in the step (3), the carbon source is a mixed gas of methane and hydrogen, the methane accounts for 10-30% of the volume of the whole mixed gas, the flow rate of the mixed gas is 20-500mL/min, the heating rate from room temperature to carbonization temperature is 1-10 ℃/min, the carbonization temperature is 600-800 ℃, and the carbonization time is 1-8 hours.
2. The method according to claim 1, wherein the organic precursor compound containing molybdenum in the process of preparing molybdenum trioxide by flame spraying in the step (1) is a compound which can be dissolved in an organic solvent and is one or more of ammonium molybdate, molybdenum acetylacetonate, molybdenum nitrate and molybdenum 2-ethylhexanoate; the solvent is combustible organic solvent, and is one or more of methanol, ethanol, xylene, benzyl alcohol and organic acid.
3. The method according to claim 1, wherein the standing time in step (2) is 12 to 24 hours; the evaporating temperature is 80-150 ℃, and the evaporating time is 4-12 hours.
4. The method according to claim 1, characterized in that:
in the step (1), the mixed gas is sprayed out by a nozzle with the diameter of 1-10mm to form flame, and air is blown into one side of the flame; the flame ignites the introduced organic solution, the precursor compounds of each component are decomposed to form oxide particles at the high temperature of the flame, the formed oxide particles leave the flame area under the drive of air, the air is blown to the whole flame area from one side of the flame by a gas distribution plate or a sieve plate with gas through holes uniformly distributed on the surface, the sum of the radial cross-sectional areas of the gas through holes on the gas distribution plate or the sieve plate is 0.1-10 square centimeters, and the air flow is 0.1-20L/min.
5. An alpha-phase molybdenum carbide catalyst carrying rhodium of noble metal prepared by the method of any one of claims 1 to 4.
6. Use of the catalyst of claim 5 in a water vapor shift reaction.
7. The process according to claim 6, wherein the water-gas shift reaction is carried out under conditions such that the mass space velocity is 30000-180000mL/g/H, the volume ratio of CO in the reaction atmosphere is 1-10%, H 2 The volume ratio of O is 2-20%, the rest is one or more than two of nitrogen or inert gases, and the reaction temperature is 120-350 ℃.
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