CN114433151B - Vanadium phosphorus oxide catalyst and preparation method and application thereof - Google Patents
Vanadium phosphorus oxide catalyst and preparation method and application thereof Download PDFInfo
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- CN114433151B CN114433151B CN202011195993.4A CN202011195993A CN114433151B CN 114433151 B CN114433151 B CN 114433151B CN 202011195993 A CN202011195993 A CN 202011195993A CN 114433151 B CN114433151 B CN 114433151B
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- vanadium phosphorus
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 41
- 238000010521 absorption reaction Methods 0.000 claims abstract description 39
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 19
- 239000003570 air Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 238000001994 activation Methods 0.000 abstract description 10
- 230000003213 activating effect Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 description 18
- 238000000465 moulding Methods 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000002243 precursor Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- -1 vanadyl pyrophosphate Chemical compound 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- B01J35/50—
-
- B01J35/613—
-
- B01J35/643—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
Abstract
A preparation method of a vanadium phosphorus oxide catalyst comprises the steps of drying and roasting a vanadium phosphorus oxide catalyst precursor, placing the vanadium phosphorus oxide catalyst precursor in a water-containing atmosphere to absorb moisture, and tabletting, forming and activating to obtain the vanadium phosphorus oxide catalyst. The invention overcomes the technical prejudice, increases the moisture absorption operation after roasting the vanadium phosphorus oxide catalyst precursor, on one hand, can improve the forming effect of the catalyst precursor, on the other hand, in the activation process, the moisture absorbed by moisture can be separated from the catalyst again in the form of water vapor, and the specific surface area of the catalyst can be increased in the separation process, so that the catalyst performance is improved.
Description
Technical Field
The invention relates to the technical field of preparation of vanadium phosphorus oxide catalysts, in particular to a preparation method of a vanadium phosphorus oxide catalyst capable of improving the specific surface area of the catalyst.
Background
The vanadium-phosphorus-oxygen catalyst is a catalyst composed of three elements of vanadium, phosphorus and oxygen, has good electron transfer function and oxygen transfer performance, is commonly used in the reaction for preparing maleic anhydride by oxidizing carbon tetrahydrocarbon, is the most effective catalyst applied to the reaction system for preparing maleic anhydride by oxidizing n-butane, and has the main active phase component of vanadyl pyrophosphate, and the catalytic performance is closely related to the preparation method. Since the first commercial use of VPO catalysts by Monsanto in 1974, the preparation process was studied intensively, see catal.rev. -sci.eng.27 (1985): 373.
the preparation of vanadium phosphorus oxide catalyst has been studied in many ways, its catalytic performance depends on its preparation method, the general preparation process is divided into adding raw materials phosphoric acid, vanadic anhydride, isobutanol and other reaction solvents, the pentavalent vanadium is reduced to tetravalent vanadium under the action of organic alcohol, the precursor crystal is finally generated, the reaction generated crystal is filtered, dried, roasted, shaped and activated, and the active component of the finally prepared vanadium phosphorus oxide catalyst is (VO) 2 P 2 O 7 。
For the vanadium phosphorus oxide catalyst, the surface property of the catalyst, the type of additive, the drying and roasting method, the method for activating the catalyst and the like have obvious influence on the catalyst performance. At present, the vanadium phosphorus oxide catalyst is also required to further improve the activity and selectivity, further improve the catalyst performance and increase the maleic anhydride yield.
The performance of the vanadium phosphorus oxygen catalyst has obvious relation with the specific surface area of the catalyst after activation molding, and the larger the specific surface area is, the better the catalyst performance is. In the process, different students adopt a method of adding a pore-expanding agent into a reaction kettle in the reaction process, and the addition and removal of the pore-expanding agent are controlled to improve the finished catalyst
US patent 5275996 discloses the removal by high temperature heat treatment under stripping gas conditions using stearic acid, citric acid, and the like as a pore template. The patent CN106582744A improves the pore canal structure of the catalyst and improves the specific surface area and the performance of the catalyst by adding a nonionic surfactant with low melting point as a pore canal template agent. The patent CN108339558A adopts trimethylolethane, trimethylolpropane, phthalic anhydride, maleic anhydride, tartaric acid, citric acid and the like as pore-expanding agents, and improves the specific surface area of the catalyst, thereby improving the activity of the catalyst.
Although the specific surface area of the catalyst can be increased by adding and removing the pore-expanding agent, the reaction operation steps are increased from the other hand, the reaction control difficulty is increased, and if the pore-expanding agent removing operation is problematic, the pore diameter collapse of the catalyst is easily caused, and the catalyst performance is reduced. In addition, the addition of a pore-expanding agent also increases the cost of the reaction.
Disclosure of Invention
Aiming at the problems that the forming effect of a vanadium phosphorus oxide catalyst precursor is poor during forming in the prior art and the improvement of the specific surface area of the vanadium phosphorus oxide catalyst is generally limited in the aspects of selecting pore canal template agents, pore-forming agents and the like, the reaction operation difficulty and the reaction cost are increased, the invention provides the vanadium phosphorus oxide catalyst, which can effectively improve the catalyst tabletting forming effect, improve the specific surface area of the activated catalyst and improve the catalyst activity through the improvement of a preparation method.
The technical purpose of the first aspect of the invention is to provide a preparation method of a vanadium phosphorus oxide catalyst, which is to dry and bake a vanadium phosphorus oxide catalyst precursor, then place the vanadium phosphorus oxide catalyst precursor in an aqueous atmosphere to absorb moisture, and then perform tabletting, forming and activating to obtain the vanadium phosphorus oxide catalyst.
It is generally understood by those skilled in the art that during the production of vanadium phosphorus oxide catalysts, operational attention is paid to avoiding water absorption, as the vanadium phosphorus oxide catalyst precursor component VOHPO is generally considered 4 ·0.5H 2 O and active phase component (VO) 2 P 2 O 7 Decomposition can occur in water, thereby deactivating the catalyst. However, in the invention, the technical prejudice is overcome, and the method innovatively adopts a small amount of moisture absorption of the calcined non-formed catalyst precursor in an atmosphere containing a certain humidity, so that the catalyst forming effect is improved, a small amount of water absorbed in the activation process can be removed from the formed catalyst, the specific surface area of the activated catalyst can be improved, and the catalyst performance is improved.
Further, the moisture absorption rate of the catalyst precursor is 0.01% -80%, preferably 0.5% -20%, and most preferably 1% -10%, and the moisture absorption rate refers to the ratio of the moisture absorption amount of the catalyst precursor after moisture absorption to the weight of the catalyst precursor before moisture absorption.
Further, the relative humidity of the gas in the aqueous atmosphere is 1% -100%, preferably 10% -90%, and most preferably 50% -80%.
Further, the gas of the aqueous atmosphere is selected from at least one of air, nitrogen or inert gas, preferably air or nitrogen.
Further, the moisture absorption is performed at a temperature of 0 ℃ to 100 ℃, preferably 10 ℃ to 50 ℃, and most preferably 15 ℃ to 35 ℃.
Further, the time of moisture absorption is 2-48 hours, preferably 4-24 hours, and most preferably 6-12 hours.
Further, the moisture absorption operation is performed such that the thickness of the catalyst precursor powder placement layer is 1cm to 30cm, preferably 1 to 10cm, more preferably 2cm to 5cm.
Further, the moisture absorption can be performed in an atmospheric environment, preferably in a constant temperature and humidity machine with adjustable humidity and temperature.
Further, the vanadium phosphorus oxide catalyst precursor is prepared by a liquid phase method, the preparation of the vanadium phosphorus oxide catalyst precursor by the liquid phase method is a technology well known to a person skilled in the art, and the method generally refers to a method for preparing a vanadium phosphorus oxide catalyst precursor solution by taking phosphoric acid and vanadium oxide as raw materials and reacting the raw materials in an organic solvent in the prior art. Specifically, the catalyst is generally prepared by taking an organic solvent as a solvent and taking vanadium pentoxide and phosphoric acid as raw materials, and as a more preferable implementation mode, an auxiliary agent is also added in the preparation process of the vanadium phosphorus oxide catalyst precursor, wherein the auxiliary agent comprises, but is not limited to, at least one salt containing Co, ni, zn, bi, zr, cu, li, K, ca, mg, ti, la, mo, nb, B, fe, cr or Ce; the organic solvent is at least one selected from isoamyl alcohol, isobutanol, isopropanol, benzyl alcohol and n-octanol.
As a more specific preferred embodiment, the preparation of the vanadium phosphorus oxide catalyst precursor includes, but is not limited to, the preparation methods disclosed in patent applications CN105749941A, CN104549393A, CN104607220a and CN104549392 a.
Further, the drying temperature is 80-170 ℃ and the drying time is 6-12 hours; the roasting temperature is 100-600 ℃, preferably 150-450 ℃, and most preferably 200-300 ℃; the roasting time is 1-24 hours, preferably 3-10 hours. The roasting atmosphere is air, nitrogen, inert gas or a mixture of inert gas and air.
Further, the activation is a technique well known to those skilled in the art, specifically, is carried out under an atmosphere of one or a combination of a mixture of nitrogen/air, a mixture of water vapor/air, a mixture of n-butane/air or a mixture of cyclohexane/air, the activation temperature is 350 to 450 ℃, preferably 375 to 425 ℃, the activation time is 5 to 40 hours, preferably 12 to 20 hours
The technical purpose of the second aspect of the invention is to provide the vanadium phosphorus oxide catalyst prepared by the method. The catalyst prepared by the method firstly absorbs moisture of the precursor in a certain humidity atmosphere, so that the catalyst forming effect can be improved, and in the catalyst activation process, a small amount of moisture contained in the formed catalyst can be separated from the catalyst again in a water vapor form, and the specific surface area in the catalyst can be increased in the separation process, so that the catalyst performance is improved.
The technical object of the third aspect of the present invention is to provide the use of the above vanadium phosphorus oxide catalyst for the reaction of n-butane oxidation to maleic anhydride. Specifically, the reaction conditions are generally: the reaction temperature is 380-450 ℃, the pressure is normal pressure-0.5 MPa, and the space velocity of the n-butane mixed gas is 1000-3500 h -1 The concentration of the n-butane is 1.0-1.8% (volume percent).
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The invention overcomes the technical prejudice, increases the moisture absorption operation after roasting the vanadium phosphorus oxide catalyst precursor, on one hand, can improve the forming effect of the catalyst precursor, on the other hand, in the activation process, the moisture absorbed by moisture can be separated from the catalyst again in the form of water vapor, and the specific surface area of the catalyst can be increased in the separation process, so that the catalyst performance is improved.
(2) The specific surface area of the catalyst obtained by the method is increased, the influence of the precursor crystallization process caused by the process of adding and removing the pore canal template agent and the pore expanding agent can be avoided, and the crystal performance and the catalyst activity performance of the catalyst precursor are ensured.
(3) The water is used as a safe and environment-friendly substance, so that the environmental pollution caused by other pore canal templates and pore expanding agents can be effectively avoided, the moisture-containing gas is used as a medium, and the small amount of moisture absorption method of the baked catalyst precursor powder does not have extra operation influence on the subsequent forming and activating processes.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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.
The specific surface area and pore size of the catalysts prepared in the following examples and comparative examples were measured using an AUTOSORB3B type full-automatic specific surface area and pore size distribution instrument of Quantachrome company, U.S.A.
Vanadium phosphorus oxide catalyst precursors prepared in a liquid phase process were used in the following examples and comparative examples:
in a reaction kettle, adding 649mL of isobutanol solution, 29.53g of vanadium pentoxide, 0.3g of auxiliary ferric nitrate hexahydrate, 0.5g of auxiliary zirconium nitrate, 34.98g of concentrated phosphoric acid, stirring, raising the reaction temperature and keeping at 100 ℃, carrying out reflux reaction, keeping the reflux time for 6 hours, cooling the reaction liquid to room temperature, carrying out vacuum filtration, and leaching a filter cake with a small amount of isobutanol three times. And drying the filter cake in a 100 ℃ oven for 12 hours, and finally roasting in a muffle furnace for 5 hours at 250 ℃ to obtain the black brown catalyst precursor.
The above vanadium phosphorus oxide catalyst precursor was subjected to different subsequent treatments in the following examples and comparative examples, respectively:
example 1
The obtained catalyst precursor is placed in a constant temperature and humidity machine, a gas medium in the constant temperature and humidity machine is air, the thickness of a catalyst layer is 2cm, the temperature is 25 ℃, the air humidity is 80%, the moisture absorption time is 12h, and the moisture absorption rate is measured to be 12%. The catalyst precursor after moisture absorption is pressed into tablets for molding, and the forming rate of the catalyst precursor after moisture absorption is higher than that of the catalyst precursor after moisture absorption, namely, the catalyst precursor after moisture absorption is pressed into tablets for molding in the tablet molding process, so that the catalyst precursor after moisture absorption is easy to mold and the molding effect is good; after molding, the mixture is placed in a tubular reactor and is treated with nitrogen in an inert gas nitrogen atmosphereGas space velocity 800h -1 Heating to 3 ℃/min, heating the activation temperature from room temperature to 425 ℃ for roasting treatment, and keeping the temperature at 425 ℃ for 6 hours, and ending the activation process to obtain the vanadium phosphorus oxide catalyst C1 in a green state. The specific surface area and pore size results are shown in Table 1.
Example 2
The obtained catalyst precursor is placed in a constant temperature and humidity machine, a gas medium in the constant temperature and humidity machine is air, the thickness of a catalyst layer is 4cm, the temperature is 25 ℃, the air humidity is 50%, the moisture absorption time is 8 hours, and the moisture absorption rate is measured to be 5%. The subsequent operation is the same as in example 1, the hygroscopic precursor powder has good molding effect and high molding rate; and obtaining the vanadium phosphorus oxide catalyst C2. The specific surface area and pore size results are shown in Table 1.
Example 3
Placing the obtained catalyst precursor in a tray, wherein the thickness of a material layer is 2cm, placing the tray in an indoor atmospheric environment, and standing for 12 hours; the temperature changes from 15 ℃ to 20 ℃ during standing, the indoor humidity changes from 40% to 50%, and the moisture absorption rate is measured to be 6% after the completion of standing. The subsequent operation is the same as in example 1, the hygroscopic precursor powder has good molding effect and high molding rate; and obtaining the vanadium phosphorus oxide catalyst C3. The specific surface area and pore size results are shown in Table 1.
Example 4
The obtained catalyst precursor is placed in a constant temperature and humidity machine, the gas medium in the constant temperature and humidity machine is nitrogen, the thickness of a catalyst layer is 4cm, the temperature is 25 ℃, the relative humidity of gas is 50%, the moisture absorption time is 10 hours, and the measured moisture absorption rate is 7%. The subsequent operation is the same as in example 1, the hygroscopic precursor powder has good molding effect and high molding rate; and obtaining the vanadium phosphorus oxide catalyst C4. The specific surface area and pore size results are shown in Table 1.
Example 5
The obtained catalyst precursor is placed in a constant temperature and humidity machine, a gas medium in the constant temperature and humidity machine is air, the thickness of a catalyst layer is 6cm, the temperature is 25 ℃, the relative humidity of gas is 40%, the moisture absorption time is 4 hours, and the measured moisture absorption rate is 2%. The subsequent operation is the same as in example 1, the hygroscopic precursor powder has good molding effect and high molding rate; and obtaining the vanadium phosphorus oxide catalyst C5. The specific surface area and pore size results are shown in Table 1. Example 6
The obtained catalyst precursor is placed in a constant temperature and humidity machine, a gas medium in the constant temperature and humidity machine is air, the thickness of a catalyst layer is 2cm, the temperature is 25 ℃, the relative humidity of gas is 80%, the moisture absorption time is 24 hours, and the moisture absorption rate is 22% measured. The subsequent operation is the same as in example 1, the hygroscopic precursor powder has good molding effect and high molding rate; and obtaining the vanadium phosphorus oxide catalyst C6. The specific surface area and pore size results are shown in Table 1.
Comparative example 1
The obtained precursor powder is directly subjected to tabletting and activating operations which are the same as those of the embodiment 1 without moisture absorption, the precursor powder is not easy to form in the tabletting process, the operation difficulty is increased, and the forming rate is low; and obtaining the vanadium phosphorus oxide catalyst D. The specific surface area and pore size results are shown in Table 1.
Table 1.
The performance of the catalyst in the reaction of preparing maleic anhydride by catalyzing n-butane oxidation is measured: the conversion rate of proper interval exists in the reaction of generating maleic anhydride by n-butane under the catalysis of vanadium phosphorus oxide catalyst, and partial maleic anhydride is peroxided to generate CO along with the increase of the conversion rate of the reaction 2 And CO, the reaction selectivity gradually decreases. Since the overall yield of maleic anhydride was highest at about 85% conversion of n-butane, the overall yield at 85% conversion of n-butane was used as an evaluation criterion in the examples and comparative examples.
Crushing and screening the catalyst, taking 5mL of catalyst particles (10-20 meshes), diluting quartz sand with the same mesh number according to a ratio of 1:1, filling the catalyst particles into a stainless steel reaction tube with an inner diameter of 10mm, reacting at a temperature of 410 ℃ and a reaction pressure of 0.1MPa, wherein the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5%, and the gas space velocity is 1600h -1 The catalytic performance evaluation test was conducted under the reaction conditions of (2). The results of evaluating the catalyst performance are shown in Table 2.
Table 2.
From the results, the method provided by the invention has the advantages that after the moisture absorption operation is added to the vanadium phosphorus oxide catalyst precursor, the vanadium phosphorus oxide catalyst precursor is easier to form, the forming effect is good, the forming rate is high, and the forming operation difficulty is reduced; in addition, under the moisture absorption condition of the invention, the catalyst does not show deactivation phenomenon due to moderate moisture absorption, and the prepared catalyst has at least equivalent catalytic effect to the catalyst in the prior art.
Claims (8)
1. The preparation method of the vanadium phosphorus oxide catalyst is characterized in that a vanadium phosphorus oxide catalyst precursor is dried and roasted, then placed in an aqueous atmosphere to absorb moisture, and subjected to tabletting, shaping and activation to obtain the vanadium phosphorus oxide catalyst; wherein the drying temperature is 80-170 ℃ and the drying time is 6-12h; the roasting temperature is 200-300 ℃, and the roasting time is 1-24 hours; the relative humidity of the gas in the water-containing atmosphere is 40% -80%, the thickness of the catalyst precursor powder placement layer is 2-6 cm, and the moisture absorption rate of the catalyst precursor is 2% -22% when the moisture absorption operation is carried out.
2. The method according to claim 1, wherein the gas of the aqueous atmosphere is at least one selected from the group consisting of air, nitrogen and inert gas.
3. The method according to claim 1, wherein the moisture absorption is performed at a temperature of 0 ℃ to 100 ℃.
4. The method according to claim 1, wherein the time for moisture absorption is 2 to 48 hours.
5. The method according to claim 1, wherein the moisture absorption is performed in an atmospheric environment or in a constant temperature and humidity machine with adjustable humidity and temperature.
6. A vanadium phosphorus oxide catalyst prepared by the method of any one of claims 1-5.
7. The use of the vanadium phosphorus oxide catalyst according to claim 6 for the oxidation of n-butane to maleic anhydride.
8. The use according to claim 7, wherein the reaction conditions are: the reaction temperature is 380-450 ℃, the pressure is normal pressure-0.5 MPa, and the space velocity of the n-butane mixed gas is 1000-3500 h -1 The volume concentration of n-butane in the mixed gas is 1.0-1.8%.
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