CN115722239A - Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of eutectic solvent and application of vanadium-phosphorus-oxygen catalyst - Google Patents
Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of eutectic solvent and application of vanadium-phosphorus-oxygen catalyst Download PDFInfo
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- 230000005496 eutectics Effects 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 104
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 78
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 60
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000011541 reaction mixture Substances 0.000 claims abstract description 58
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000010438 heat treatment Methods 0.000 claims abstract description 50
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
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- 238000001816 cooling Methods 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 22
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
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- 230000004913 activation Effects 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 39
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 15
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 9
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000000811 xylitol Substances 0.000 claims description 9
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 9
- 235000010447 xylitol Nutrition 0.000 claims description 9
- 229960002675 xylitol Drugs 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
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- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- -1 vanadyl phosphate Chemical compound 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
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- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000002566 Capsicum Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 244000203593 Piper nigrum Species 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
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- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 235000013373 food additive Nutrition 0.000 description 1
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- 239000000852 hydrogen donor Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- FQUPMIQUWINAGY-UHFFFAOYSA-L magnesium ethane-1,2-diol dichloride Chemical compound [Mg+2].[Cl-].[Cl-].OCCO FQUPMIQUWINAGY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
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- 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
- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a method for preparing a vanadium phosphorus oxide catalyst by the aid of a eutectic solvent, which comprises the following steps: mixing vanadium pentoxide, isobutanol and benzyl alcohol with a eutectic solvent, and heating for reaction to obtain a reaction mixture; cooling the reaction mixture to a preset temperature, adding concentrated phosphoric acid into the reaction mixture, heating again and reacting to obtain a vanadium-phosphorus-oxygen catalyst precursor; roasting the vanadium phosphorus oxide catalyst precursor to obtain a vanadium phosphorus oxide catalyst; the eutectic solvent is formed from a metal salt and an organic alcohol. The invention also provides application of the vanadium-phosphorus-oxygen catalyst obtained by the method in preparation of maleic anhydride by selective oxidation of n-butane. The vanadium phosphorus oxide catalyst prepared by the method of the invention shows higher activity in the reaction for preparing maleic anhydride by selective oxidation of n-butane.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly relates to a method for preparing a vanadium-phosphorus-oxygen catalyst by using a eutectic solvent in an auxiliary manner, and an application of the vanadium-phosphorus-oxygen catalyst.
Background
Maleic anhydride is one of three major anhydrides in the world, unsaturated carbon-carbon double bonds and carbon-oxygen double bonds exist in molecules, and various reactions such as polymerization, amidation, addition, esterification and the like can occur, so that the maleic anhydride is used as an important chemical raw material and is mainly used for preparing unsaturated polyester, food additives, coatings, pesticides, lubricating oil additives, surfactants and the like; in addition, maleic anhydride can be used for the production of tetrahydrofuran, 1-4 butanediol, etc. by adding hydrogen. The vanadium phosphorus oxide catalyst is the only industrial catalyst for preparing maleic anhydride by selective oxidation of n-butane, but the catalyst has the problems of poor activity, low yield of target products and the like at present. Therefore, in order to improve the activity of the catalyst and the yield of the target product, a great deal of research on the preparation of the vanadium-phosphorus oxide catalyst is carried out by a great number of scholars at home and abroad.
In patent application CN113058625A, a vanadium phosphorus oxide catalyst precursor and a choline chloride-alcohol eutectic solvent are subjected to co-ball milling, so that the activity of the catalyst and the selectivity of a target product are improved. Patent application CN111701608A proposes a preparation method for preparing a vanadium phosphorus oxide catalyst with the assistance of hydrotalcite, which realizes the regulation of the acidity and alkalinity of the catalyst by introducing hydrotalcite with different acidity and alkalinity, and the activity of the vanadium phosphorus oxide catalyst and the selectivity of maleic anhydride are improved to a certain extent. In patent application CN104971750A, alkali metals Na, K, rb, cs or their mixture are used as an assistant to improve the catalytic performance of vanadium phosphorus oxide catalyst, and researches show that the addition of a proper amount of alkali metal can improve the selectivity of maleic anhydride. However, although the activity of the vanadium phosphorus oxide catalyst and the selectivity of the target product are improved to some extent by modifying the vanadium phosphorus oxide catalyst in the prior art, double regulation of structure and electrons cannot be realized, organic and metal regulation needs to be carried out in two steps, the effect is not significant, and the steps are complicated.
Therefore, it is urgently needed to provide a method for preparing a vanadium phosphorus oxide catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a vanadium-phosphorus-oxygen catalyst by using a eutectic solvent in an auxiliary manner and also provides an application of the vanadium-phosphorus-oxygen catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing a vanadium-phosphorus-oxygen catalyst with the assistance of a eutectic solvent, which comprises the following steps:
(1) Mixing vanadium pentoxide, isobutanol and benzyl alcohol with a eutectic solvent, and heating for reaction to obtain a reaction mixture;
(2) Cooling the reaction mixture to a preset temperature, adding concentrated phosphoric acid into the reaction mixture, heating again and reacting to obtain a vanadium-phosphorus-oxygen catalyst precursor;
(3) Roasting the vanadium phosphorus oxide catalyst precursor to obtain a vanadium phosphorus oxide catalyst;
wherein the eutectic solvent in step (1) is formed from a metal salt and an organic alcohol.
Further, the eutectic solvent is a uniform and transparent mixture formed by mixing and stirring the metal salt and the organic alcohol and heating the mixture to 50-100 ℃, wherein the molar ratio of the metal salt to the organic alcohol is 1 (1-6).
Further, the metal salt is at least one of magnesium chloride, magnesium nitrate, cerium chloride, ammonium cerium nitrate, copper chloride and cerium nitrate, and the organic alcohol is at least one of ethylene glycol, glycerol and xylitol.
Further, the metal salt is at least one of magnesium chloride, magnesium nitrate and copper chloride.
Further, in step (1):
the reaction temperature is 100-180 ℃, and the reaction time is 1-6 h;
the volume ratio of the benzyl alcohol to the isobutanol is 1 (3-5);
the molar ratio of the metal in the metal salt to the vanadium in the vanadium pentoxide is (0.0001-0.02): 1.
Further, in step (2):
and cooling the reaction mixture to 60-100 ℃, wherein the reaction temperature of the reaction mixture and the concentrated phosphoric acid is 100-150 ℃, the reaction time is 8-16 h, and the mass concentration of the concentrated phosphoric acid is more than or equal to 80%.
Further, in step (3):
the roasting temperature of the vanadium phosphorus oxygen catalyst precursor is 420-440 ℃, and the roasting time is 10-24 h.
Further, in step (3):
the roasting atmosphere is nitrogen atmosphere, or the mixed atmosphere of n-butane and air, or the mixed atmosphere of n-butane, oxygen and nitrogen.
Further, in step (3):
before roasting, firstly, tabletting and molding the vanadium-phosphorus-oxygen catalyst precursor, then grinding and screening to obtain precursor particles of 10-50 meshes, then placing the precursor particles in a fixed bed reactor, and carrying out high-temperature in-situ activation in the roasting atmosphere to obtain the vanadium-phosphorus-oxygen catalyst.
The invention also provides an application of the vanadium phosphorus oxide catalyst obtained by the method in the preparation of maleic anhydride by selective oxidation of n-butane, wherein,
the reaction conditions for preparing maleic anhydride by selective oxidation of n-butane are as follows: the reaction temperature is 400-550 ℃, the reaction pressure is 0.1-0.3 MPa, and the space velocity of the n-butane mixed gas is 1000h -1 ～2500h -1 And the concentration of the n-butane is 1.3wt% -1.8 wt%.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) The metal alcohol eutectic solvent has simple synthesis and low cost, and compared with a vanadium phosphorus oxide catalyst without the addition of the eutectic solvent and the addition of a traditional auxiliary agent, the catalyst shows higher activity in the reaction of preparing maleic anhydride by selective oxidation of n-butane.
(2) The preparation method adopts the metal-based alcohol eutectic solvent to strengthen the preparation of the vanadium-phosphorus-oxygen catalyst, and the oxidation-reduction characteristic, the surface acidity-basicity, the P/V and the like of the catalyst are changed after the eutectic solvent is added, so that the activity of the catalyst is effectively improved.
(3) The eutectic solvent auxiliary agent consists of metal chloride and organic alcohol, and a strong hydrogen bond effect exists between the metal chloride and the organic alcohol, so that compared with the traditional auxiliary agent, the eutectic solvent can induce the growth behavior of a precursor, and the eutectic solvent is decomposed in the activation process of the precursor, so that the specific surface area of the catalyst is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1A is a scanning electron micrograph of a vanadium phosphorus oxide catalyst precursor obtained in example 4 of the present invention;
FIG. 1B is a scanning electron micrograph of a vanadium phosphorus oxide catalyst precursor obtained in comparative example 10 according to the present invention;
FIG. 2A is a scanning electron micrograph of a vanadium phosphorus oxide catalyst obtained in example 4 of the present invention;
fig. 2B is a scanning electron micrograph of the vanadium phosphorus oxide catalyst obtained in comparative example 10 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments of the present invention are described in further detail with reference to the accompanying drawings.
The invention provides a method for preparing a vanadium-phosphorus-oxygen catalyst with the assistance of a eutectic solvent, which comprises the following steps:
(1) Mixing vanadium pentoxide, isobutanol and benzyl alcohol with a eutectic solvent, and heating to react to obtain a reaction mixture, wherein the eutectic solvent is formed by a metal salt and an organic alcohol.
In the present invention, the method of forming the eutectic solvent by the metal salt and the organic polyol is the prior art, and the preparation can be performed by referring to the method disclosed in the prior art by the skilled person, for example, the following method is performed: specifically, metal salt and organic alcohol are mixed and stirred and heated to 50-100 ℃ to form a uniform and transparent mixture, wherein the molar ratio of the metal salt (hydrogen bond acceptor) to the organic alcohol (hydrogen bond donor) is 1 (1-6). The metal salt is at least one of magnesium chloride, magnesium nitrate, cerium chloride, ammonium ceric nitrate, copper chloride and cerium nitrate, and preferably, the metal salt is at least one of magnesium chloride, magnesium nitrate and copper chloride. The organic alcohol is at least one of ethylene glycol, glycerol and xylitol.
The reaction temperature is 100-180 ℃, preferably 130-140 ℃, and the reaction time is 1-6 h, preferably 3-5 h. The volume ratio of the benzyl alcohol to the isobutanol is 1 (3-5), the molar ratio of the metal in the metal salt to the vanadium in the vanadium pentoxide is (0.0001-0.02): 1, and preferably (0.005-0.01): 1.
(2) And (3) cooling the reaction mixture to a preset temperature, then adding concentrated phosphoric acid into the reaction mixture, heating again, reacting, filtering, washing and drying the product to obtain the vanadium-phosphorus-oxygen catalyst precursor.
The temperature of the reaction mixture is reduced to 60-100 ℃, the reaction temperature of the reaction mixture and concentrated phosphoric acid is 100-150 ℃, the reaction time of heating reflux is 8-16 h, and the mass concentration of the concentrated phosphoric acid is more than or equal to 80%.
(3) And roasting the vanadium-phosphorus-oxygen catalyst precursor to obtain the vanadium-phosphorus-oxygen catalyst.
The roasting temperature of the vanadium-phosphorus-oxygen catalyst precursor is 420-440 ℃, and the roasting time is 10-24 h. The roasting atmosphere is nitrogen atmosphere, or the mixed atmosphere of normal butane and air, or the mixed atmosphere of normal butane, oxygen and nitrogen, the volume ratio of normal butane to air (0.8-1.8) is 100, and the volume ratio of normal butane, oxygen and nitrogen (0.8-1.8) is 10-25) to 75-85.
In order to facilitate the effect evaluation of the catalyst, the roasting step can be carried out after the vanadyl phosphate precursor is formed, and the roasted vanadyl phosphate precursor is directly used for the effect evaluation of the catalyst; or the catalyst can be calcined and then molded, and then used for evaluating the effect of the catalyst.
In a preferred embodiment, before roasting, firstly, the vanadium phosphorus oxygen catalyst precursor is tableted and molded, then is ground and sieved to obtain precursor particles with the size of 10-50 meshes, preferably 20-40 meshes, then the precursor particles with the volume of 1-5 ml, preferably 2-4 ml are measured and placed in a fixed bed reactor, and are activated in situ at high temperature in the roasting atmosphere to obtain the vanadium phosphorus oxygen catalyst.
The invention also provides an application of the vanadium phosphorus oxide catalyst obtained by the method in the preparation of maleic anhydride by selective oxidation of n-butane, wherein the reaction conditions for preparing the maleic anhydride by selective oxidation of the n-butane are as follows: the reaction temperature is 400-550 ℃, the reaction pressure is 0.1-0.3 MPa, and the space velocity of the n-butane mixed gas is 1000h -1 ～2500h -1 And the concentration of the n-butane is 1.3wt% -1.8 wt%.
The following example illustrates the eutectic solvent assisted preparation of a vanadium phosphorus oxide catalyst. The compounds in the following examples can be prepared directly according to the existing methods, but of course, in other examples, they can be directly commercially available, and are not limited thereto.
Wherein the organic alcohol is Ethylene Glycol (EG), glycerol (GL) and Xylitol (XL), for example, the eutectic solvent of magnesium chloride and ethylene glycol is represented by MgCl 2 The eutectic solvent of/EG, magnesium chloride and xylitol is represented by MgCl 2 Eutectic solvent of/XL, magnesium nitrate and glycerol is represented as Mg (NO) 3 ) 2 The eutectic solvent of nitric acid and ethylene glycol is Ce (NO) 3 ) 3 The eutectic solvent of/EG, chlorinated Pepper and ethylene glycol is represented by CeCl 2 /EG, cerium ammonium nitrate with ethylene glycol as Ce (NH) 4 ) 2 (NO 3 ) 6 /EG。
Example 1
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 3.5mmol of ethylene glycol and 1.75mmol of CeCl are added 2 Eutectic solvent formed (CeCl) 2 /EG), mechanically stirred at 135 ℃ in the reverse directionAnd (3) obtaining a reaction mixture after 3 hours, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12 hours under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
Tabletting and molding the vanadium phosphorus oxide catalyst precursor, grinding and screening to obtain particles of 20-40 meshes, measuring 3mL of catalyst precursor particles, and placing the catalyst precursor particles in a fixed bed reactor. At the airspeed of 2000h -1 Raw material gas (C) 4 H 10 /O 2 /N 2 Activating in the temperature of a fixed bed in a speed of 2 ℃/min from room temperature to 430 ℃ for 12 hours, and then reducing the temperature of the bed to 420 ℃ to prepare maleic anhydride by n-butane oxidation.
The reaction tail gas is analyzed on line by gas chromatography, the conversion rate of the obtained n-butane is 88.7 percent, the selectivity of the maleic anhydride is 65.5 percent, and the mass yield of the maleic anhydride is 98 percent.
Example 2
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 3.5mmol of ethylene glycol and 1.75mmol of Ce (NO) are added 3 ) 3 Formed eutectic solvent (Ce (NO) 3 ) 3 and/EG), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 86.2%, the selectivity of maleic anhydride was 64.8%, and the mass yield of maleic anhydride was 94.2%.
Example 3
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 3.5mmol of glycerol and 1.75mmol of Mg (NO) are added 3 ) 2 Eutectic solvent formed (Mg (NO) 3 ) 2 GL), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 93.1%, the selectivity of maleic anhydride was 64.2% and the mass yield of maleic anhydride was 101%.
Example 4
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 3.5mmol of ethylene glycol and 1.75mmol of MgCl are added 2 Eutectic solvent formed (MgCl) 2 and/EG), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 87.6%, the selectivity of maleic anhydride was 68.0%, and the mass yield of maleic anhydride was 100.5%.
Example 5
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 3.5mmol of xylitol and 1.75mmol of MgCl are added 2 Formed of lowEutectic solvent (MgCl) 2 /XL) under the condition of 135 ℃ and mechanically stirring for reaction for 3 hours to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12 hours under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 86%, the selectivity of maleic anhydride was 70% and the mass yield of maleic anhydride was 101%.
Example 6
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 3.5mmol of ethylene glycol and 1.75mmol of Ce (NH) are added 4 ) 2 (NO 3 ) 6 Formed eutectic solvent (Ce (NH) 4 ) 2 (NO 3 ) 6 and/EG), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 88%, the selectivity of maleic anhydride was 71%, and the mass yield of maleic anhydride was 105%.
Example 7
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 45ml of isobutanol are mixed and then 3.5mmol of ethylene glycol and 3.5mmol of MgCl are added 2 Eutectic solvent formed (MgCl) 2 /EG), mechanically stirring the mixture at 140 ℃ for 5 hours to obtain a reaction mixture, then cooling the reaction mixture to 100 ℃, and adding 7.23ml of substancesHeating phosphoric acid with the weight percentage of 85 percent to 150 ℃, heating and refluxing for 8 hours under continuous stirring, filtering, washing and drying the obtained product to prepare the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 84%, the selectivity of maleic anhydride was 72%, and the mass yield of maleic anhydride was 102%.
Example 8
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 75ml of isobutanol are mixed and then 3.5mmol of ethylene glycol and 0.584mmol of Mg (NO) are added 3 ) 2 Eutectic solvent formed (Mg (NO) 3 ) 2 and/EG), mechanically stirring and reacting for 6h at 180 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 60 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 100 ℃, heating and refluxing for 16h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 86%, the selectivity of maleic anhydride was 70% and the mass yield of maleic anhydride was 102%.
Comparative example 1
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 Mixing 15ml of benzyl alcohol and 60ml of isobutanol, adding 3.5mmol of ethylene glycol, mechanically stirring at 135 ℃ for reaction for 3h to obtain a reaction mixture, cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating under continuous stirring for reflux for 12h, filtering, washing and drying the obtained product to obtain the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 83.8%, the selectivity of maleic anhydride was 65.2%, and the mass yield of maleic anhydride was 92.2%.
Comparative example 2
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 0.8mmol of MgCl are added 2 Mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 81.6%, the selectivity of maleic anhydride was 66.7%, and the mass yield of maleic anhydride was 91.8%.
Comparative example 3
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 0.8mmol of MgCl is added in succession 2 And 3.5mmol of ethylene glycol, performing mechanical stirring reaction for 3 hours at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12 hours under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 83.2%, the selectivity of maleic anhydride was 65.7%, and the mass yield of maleic anhydride was 92.2%.
Comparative example 4
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzeneMixing methanol and 60ml of isobutanol, then mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 79.5%, the selectivity of maleic anhydride was 66.0%, and the mass yield of maleic anhydride was 88.4%.
Comparative example 5
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 0.9mmol of ethylene glycol and 0.9mmol of ErCl are added 3 Eutectic solvent formed (ErCl) 3 /EG), mechanically stirring and reacting at 135 ℃ for 3h to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product to obtain the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 50.6%, the selectivity of maleic anhydride was 66.4%, and the mass yield of maleic anhydride was 56.7%.
Comparative example 6
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 1.0mmol of ethylene glycol and 1.0mmol of SnCl are added 4 Eutectic solvent formed (SnCl) 4 /EG), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, and heating back under continuous stirringAfter flowing for 12h, filtering, washing and drying the obtained product to prepare the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 53.0%, the selectivity of maleic anhydride was 68.0%, and the mass yield of maleic anhydride was 60.7%.
Comparative example 7
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 1.1mmol of ethylene glycol and 1.1mmol of YCl are added 3 Eutectic solvent (YCl) formed 3 and/EG), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 55.5%, the selectivity of maleic anhydride was 66.2%, and the mass yield of maleic anhydride was 62.0%.
Comparative example 8
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 1.3mmol of ethylene glycol and 1.3mmol of BaCl are added 2 Eutectic solvent formed (BaCl) 2 and/EG), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 65.1%, the selectivity of maleic anhydride was 72.3%, and the mass yield of maleic anhydride was 79.5%.
Comparative example 9
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol were mixed and then 1.2mmol of glycerol and 1.2mmol of CoCl were added 2 Eutectic solvent formed (CoCl) 2 GL), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 61.3%, the selectivity of maleic anhydride was 66.2%, and the mass yield of maleic anhydride was 68.5%.
Comparative example 10
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol are mixed and then 3.5mmol of 1-4-butanediol and 1.75mmol of MgCl are added 2 Eutectic solvent formed (MgCl) 2 BDO), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 66.50%, the selectivity of maleic anhydride was 63.45% and the mass yield of maleic anhydride was 71.18%.
Comparative example 11
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol were mixed and then 1.3mmol of ethylene glycol and 1.1mmol of CoCl were added 2 Eutectic solvent formed (CoCl) 2 and/EG), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 71.7%, the selectivity of maleic anhydride was 66.7%, and the mass yield of maleic anhydride was 80.6%.
Comparative example 12
(1) Preparation of vanadium phosphorus oxide catalyst precursor
9.094g of V 2 O 5 15ml of benzyl alcohol and 60ml of isobutanol were mixed and then 1.2mmol of 1-4-butanediol and 1.2mmol of CoCl were added 2 Eutectic solvent formed (CoCl) 2 BDO), mechanically stirring and reacting for 3h at 135 ℃ to obtain a reaction mixture, then cooling the reaction mixture to 80 ℃, adding 7.23ml of phosphoric acid with the mass fraction of 85%, heating to 135 ℃, heating and refluxing for 12h under continuous stirring, filtering, washing and drying the obtained product, and obtaining the vanadium-phosphorus-oxygen catalyst precursor.
(2) Catalyst precursor activation and evaluation
The procedure for activation and evaluation of the catalyst precursor was the same as in example 1. The conversion of n-butane obtained was 66.5%, the selectivity of maleic anhydride was 64.5%, and the mass yield of maleic anhydride was 72.4%.
As can be seen from the comparison of example 4 with comparative examples 1, 2 and 3, mgCl is used in example 4 2 Vanadium phosphorus oxygen catalyst (VPO-MgCl) obtained by using/EG as eutectic solvent 2 EG) was about 3 to 6% higher than in comparative examples 1-3, mgCl 2 Eutectic solvent for EGThe addition of (2) is beneficial to the improvement of the performance of the catalyst. This is because of MgCl 2 the/EG eutectic solvent not only promotes the generation of active crystal faces of the catalyst, but also promotes gamma-VOPO 4 And (4) generation of a crystalline phase. Raman spectroscopy confirmed this hypothesis, mgCl 2 In the presence of an/EG eutectic solvent, beta-VOPO 4 And gamma-VOPO 4 The relative strength of the phases is higher than other catalysts, indicating that eutectic solvents can modulate the composition of the crystalline phases. Notably, VPO-MgCl 2 of/EG (VO) 2 P 2 O 7 The characteristic peak of the crystal phase shows a splitting peak, which indicates that the microstructure of the catalyst is different and is probably caused by V = O bonds with different angles.
Table 1 XRD characterization results of catalyst precursors in example 4 and comparative examples 1-3
The XRD characterization results of the vanadium phosphorus oxide catalyst precursor of example 4 and comparative examples 1, 2 and 3 are shown in table 1. Wherein the vanadium-phosphorus-oxygen catalyst precursors in example 4 and comparative examples 1 to 3 are represented as PVPO-MgCl, respectively 2 /EG、PVPO-EG、PVPO-MgCl 2 And PVPO-MgCl 2 And EG. Example 4 use of a eutectic solvent of the invention MgCl 2 and/EG preparing a vanadium-phosphorus-oxygen catalyst precursor. In comparative example 1, only organic alcohol ethylene glycol was used, but no metal salt was used. In comparative example 2, only the metal salt was used, but the organic alcohol glycol was not used. In example 3, although magnesium chloride and ethylene glycol were used simultaneously, they were added separately to the reaction mass and did not form a eutectic solvent, mgCl 2 The reaction of the two is not carried out in the form of eutectic solvents.
As can be seen from Table 1, the growth process of the precursor is influenced by the single hydrogen donor and the eutectic solvent as the auxiliary agents, and the relative content of crystal faces and the size of crystal grains are changed, which is probably because the specific adsorption is formed on the surfaces between different auxiliary agent molecules and the catalyst to regulate the growth process of the crystal. When EG alone was added in comparative example 1, I (001) /I (130) The highest ratio, probably forming an unstable complex with vanadium during synthesis of the precursor, promotes the growth of the (001) crystal plane. PVPO-MgCl 2 /EG and PVPO-MgCl 2 The former of the two precursors EG has smaller grain size, which is more beneficial to the topological transformation of crystal phase, and shows that the existence of hydrogen bond network in eutectic solvent can make the crystal grow to the preferred direction.
Taking example 4 and comparative example 10 as examples, FIGS. 1A and 1B show the addition of ethylene glycol magnesium chloride eutectic solvent (MgCl) during the preparation of example 4 and comparative example 10, respectively 2 /EG), 1-4 butanediol magnesium chloride eutectic solvent (MgCl) 2 BDO) to obtain a microscopic morphology picture of the catalyst precursor. As can be seen from FIG. 1A, PVPO-MgCl 2 the/EG has a sheet structure and good dispersibility. And PVPO-MgCl of FIG. 1B 2 the/BDO presents a certain stacking structure and has poor dispersity due to MgCl 2 The stability of the/EG is strong, the hydrogen bond network of the EG acts with vanadium atoms, the growth of crystal nucleus can be induced to a certain extent, and the precursor keeps a regular sheet structure. This is further confirmed in FIG. 2A, where PVPO-MgCl is in a lamellar structure 2 the/EG is more likely to form fine particles after activation (FIG. 2A), which is beneficial for increasing the exposed specific surface area and thus increasing n-butane conversion. VPO-MgCl in FIG. 2B 2 the/BDO has a more regular large-sheet structure, and has larger thickness and poor dispersibility, thereby reducing the performance of the BDO. VPO-MgCl is measured by a BET full-automatic specific surface and porosity analyzer 2 /EG and VPO-MgCl 2 BDO, in order, 12.81 and 10.15, consistent with the above-described SEM-presented morphology. The higher specific surface area is beneficial to the exposure of the active sites of the catalyst, thereby improving the catalytic performance.
Comparative example 4 does not use the eutectic solvent of the present invention, and comparative examples 5 to 12 use the eutectic solvent to participate in the reaction, but the compositions of the eutectic solvents of comparative examples 5 to 12 are quite different from those of the present invention, that is, comparative examples 5 to 12 use eutectic solvents different from the scope of the present invention. Comparing the data of the conversion rate of n-butane, the selectivity of maleic anhydride, and the mass yield of maleic anhydride of examples 1 to 8 according to the present invention with those of comparative examples 4 to 12, it can be seen that the vanadium phosphorus oxide catalyst prepared using the eutectic solvent according to the present invention shows higher activity in the reaction of preparing maleic anhydride through selective oxidation of n-butane.
The formation of a catalyst precursor can be induced by the metal eutectic solvent, some eutectic solvents are not beneficial to the topological transformation of a crystalline phase in the activation process, and the increase of the number of active surfaces of the vanadium phosphorus oxide catalyst and the enrichment of P atoms on the surface are also not beneficial, so that the performance of the vanadium phosphorus oxide catalyst is poor. The eutectic solvent protected by the invention is added in the preparation process, so that not only can metal auxiliary agents and P atoms be effectively doped to enrich the surface of the catalyst, but also the precursor of the catalyst is enabled to be in fine particles after being activated, and the specific surface area of the vanadium phosphorus oxygen catalyst is improved. The addition of the eutectic solvent of the present invention induces V 5+ The crystal phase is generated, and the acid amount on the surface of the catalyst is also the highest, so that the performance of the vanadium phosphorus oxide catalyst is obviously improved.
It should be noted that, the components or steps in the above embodiments can be intersected, replaced, added or deleted, and therefore, the combination formed by reasonable permutation and combination conversion shall also belong to the protection scope of the present invention, and shall not limit the protection scope of the present invention to the above embodiments.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, of embodiments of the invention is limited to these examples; within the framework of embodiments of the invention, also combinations between technical features of the above embodiments or different embodiments are possible, and there are many other variations of the different aspects of the embodiments of the invention described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of the embodiments of the present invention are intended to be included within the scope of the embodiments of the present invention.
Claims (10)
1. The method for preparing the vanadium-phosphorus-oxygen catalyst with the assistance of the eutectic solvent is characterized by comprising the following steps of:
(1) Mixing vanadium pentoxide, isobutanol and benzyl alcohol with a eutectic solvent, and heating for reaction to obtain a reaction mixture;
(2) Cooling the reaction mixture to a preset temperature, adding concentrated phosphoric acid into the reaction mixture, heating again and reacting to obtain a vanadium-phosphorus-oxygen catalyst precursor;
(3) Roasting the vanadium phosphorus oxide catalyst precursor to obtain a vanadium phosphorus oxide catalyst;
wherein the eutectic solvent in step (1) is formed from a metal salt and an organic alcohol.
2. The method according to claim 1, wherein the eutectic solvent is a uniform transparent mixture formed by mixing and stirring the metal salt and the organic alcohol and heating to 50-100 ℃, and the molar ratio of the metal salt to the organic alcohol is 1 (1-6).
3. The method of claim 2, wherein the metal salt is at least one of magnesium chloride, magnesium nitrate, cerium chloride, cerium ammonium nitrate, copper chloride, cerium nitrate, and the organic alcohol is at least one of ethylene glycol, glycerol, and xylitol.
4. The method of claim 2 or 3, wherein the metal salt is at least one of magnesium chloride, magnesium nitrate, and copper chloride.
5. The method according to claim 1, wherein in step (1):
the reaction temperature is 100-180 ℃, and the reaction time is 1-6 h;
the volume ratio of the benzyl alcohol to the isobutanol is 1 (3-5);
the molar ratio of the metal in the metal salt to the vanadium in the vanadium pentoxide is (0.0001-0.02): 1.
6. The method of claim 1, wherein in step (2):
and cooling the reaction mixture to 60-100 ℃, wherein the reaction temperature of the reaction mixture and the concentrated phosphoric acid is 100-150 ℃, the reaction time is 8-16 h, and the mass concentration of the concentrated phosphoric acid is more than or equal to 80%.
7. The method of claim 1, wherein in step (3):
the roasting temperature of the vanadium phosphorus oxygen catalyst precursor is 420-440 ℃, and the roasting time is 10-24 h.
8. The method of claim 1, wherein in step (3):
the roasting atmosphere is nitrogen atmosphere, or the mixed atmosphere of n-butane and air, or the mixed atmosphere of n-butane, oxygen and nitrogen.
9. The method of claim 8, wherein in step (3):
before roasting, firstly, tabletting and molding the vanadium-phosphorus-oxygen catalyst precursor, then grinding and screening to obtain precursor particles of 10-50 meshes, then placing the precursor particles in a fixed bed reactor, and carrying out high-temperature in-situ activation in the roasting atmosphere to obtain the vanadium-phosphorus-oxygen catalyst.
10. Use of a vanadium phosphorus oxide catalyst obtained according to the process of any one of claims 1 to 9 in the selective oxidation of n-butane to maleic anhydride,
the reaction conditions for preparing maleic anhydride by selective oxidation of n-butane are as follows: the reaction temperature is 400-550 ℃, the reaction pressure is 0.1-0.3 MPa, and the space velocity of the n-butane mixed gas is 1000h -1 ～2500h -1 The concentration of the n-butane is 1.3wt% to 1.8wt%.
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