CN109569679B - Sodium-free vanadium-phosphorus-oxygen catalyst and preparation method thereof - Google Patents
Sodium-free vanadium-phosphorus-oxygen catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 20
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 29
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 14
- -1 oxygen ions Chemical class 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 48
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 46
- 229910001415 sodium ion Inorganic materials 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 26
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- 238000007254 oxidation reaction Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
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- 230000003647 oxidation Effects 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- 239000012018 catalyst precursor Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 15
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 12
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000540 VOPO4 Inorganic materials 0.000 claims description 4
- 238000001479 atomic absorption spectroscopy Methods 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 238000001962 electrophoresis Methods 0.000 claims description 4
- 238000009616 inductively coupled plasma Methods 0.000 claims description 4
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- 238000011034 membrane dialysis Methods 0.000 claims description 4
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- 238000004993 emission spectroscopy Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- 238000003786 synthesis reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
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- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 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
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- 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
- 230000003213 activating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 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
- 239000000575 pesticide Substances 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A sodium-free vanadium-phosphorus-oxygen catalyst is prepared by improving the local composition of matter and the influence of local trace elements on the surface of vanadium-phosphorus-oxygen catalyst to obtain sodium-free vanadium-phosphorus-oxygen catalyst, so that the surface V of vanadium-phosphorus oxide is4+The species are exposed more thoroughly, and the oxygen ions O in the crystal lattice2‑The formation rate is higher, resulting in higher catalyst activity. In addition, the sodium-free environment of the vanadium phosphorus oxide surface makes V4+The local charge density and the acidity of the active center of the species are more stable, and the target phase state intermediate structure formed between the n-butane molecule and the active center is more single, so that the selectivity of the catalyst is higher. The n-butane conversion activity of the sodium-free vanadium phosphorus oxide catalyst is greatly improved to more than 94%, and the selectivity of maleic anhydride is improved to more than 71%; and the stability of different batches of reactions is better.
Description
Technical Field
The invention relates to a sodium-free vanadium-phosphorus oxide catalyst and a preparation method thereof, wherein the sodium-free vanadium-phosphorus oxide catalyst is suitable for heterogeneous selective oxidation of short-chain alkane, and is particularly suitable for preparing maleic anhydride by gas-phase oxidation of n-butane.
Background
Maleic anhydride, called maleic anhydride for short, is the third world organic anhydride second only to phthalic anhydride and acetic anhydride. The maleic anhydride is an important chemical intermediate, and due to the presence of a conjugated maleic acyl group in a molecular structure, the maleic anhydride has high activity and can perform various chemical reactions such as addition, self-polymerization, amidation, hydrogenation, alkylation, esterification, hydration, redox and the like.
One of the most important uses of maleic anhydride is in the production of Unsaturated Polyester Resins (UPR) in the glass fiber reinforced plastic industry; maleic anhydride can also be used to produce 1, 4-Butanediol (BDO), Tetrahydrofurane (THF) and gamma-butyrolactone (GBL) in hydrogenated products; can also be applied to the production of tartaric acid, succinic acid, malic acid, tetrahydrophthalic anhydride and the like; meanwhile, the maleic anhydride deep-processed product is also used for producing high-added-value fine chemical products in the fields of coatings, lubricating oil additives, pesticides, medicines and the like.
The preparation of maleic anhydride by selective oxidation of n-butane is the only industrialized selective oxidation reaction of low-carbon alkane, and VPO catalysts are the most effective catalysts for preparing maleic anhydride by selective oxidation of n-butane, and the main component of the VPO catalysts is vanadyl pyrophosphate. Since the selective oxidation of n-butane is a structure-sensitive reaction, the different crystal structures and surface states of the catalyst determine the selectivity and conversion of maleic anhydride. Since the discovery that the complex structure of vanadium phosphorus oxide catalysts can effectively select n-butane oxide to prepare maleic anhydride, a great deal of research on the catalysts is carried out; the catalytic performance of vanadium phosphorus oxide catalysts is very sensitive to the preparation conditions. The differences in the preparation methods and the introduction of auxiliaries and additives lead to a large difference in the catalytic activity of the finally obtained catalyst.
The VPO catalyst is a composite oxide catalyst with a complex microstructure, the catalytic activity of the VPO catalyst is greatly related to the structure and the composition of the VPO catalyst, and the preparation process of the VPO catalyst has great influence on the catalytic performance. In order to improve the activity and selectivity of the vanadium phosphorus oxide catalyst and improve the economic benefit of the existing device, people carry out intensive research on the preparation method of the vanadium phosphorus oxide catalyst.
The reaction for preparing maleic anhydride by n-butane oxidation belongs to lattice oxygen oxidation reaction from the principle, and the functions of oxygen adsorption and oxygen storage capacity of the catalyst in butane oxidation are very important.
CN105709790A describes a preparation method of a vanadium phosphorus oxide catalyst for preparing maleic anhydride by butane oxidation. The method starts from the aspect of catalyst physical property, and obtains the small-crystal vanadium-phosphorus-oxygen catalyst by adding modifiers such as formamide and the like. The vanadium-phosphorus-oxygen catalyst prepared by the method has the normal butane conversion rate of 54-87% and the maleic anhydride selectivity of 59-66%.
CN1345630A describes a preparation method of a catalyst for preparing maleic anhydride by butane oxidation, which starts with the addition of catalyst auxiliaries and the improvement of physical properties, and obtains a modified vanadium-phosphorus-oxygen catalyst by adding auxiliaries such as Zn and rare earth element oxides. Then modified starch, stearic acid and the like are added in the forming process to improve the pore structure of the catalyst. The conversion rate of the catalyst n-butane obtained by the method is 76-86%.
CN104549392A describes a method for preparing a vanadium phosphorus oxygen catalyst, which starts from the aspect of catalyst preparation process, the catalyst precursor is synthesized in a fluidized bed reactor, and the materials are in a "fluidized state" during the synthesis process, thereby increasing the uniformity of the catalyst.
The invention starts from the aspects of the type of an auxiliary agent, the preparation process, the physical property characteristics and the like of the vanadium phosphorus oxide catalyst and improves the performance of the catalyst, but the catalyst is not improved from the aspects of the local substance composition and the local trace element influence on the surface of the catalyst.
Disclosure of Invention
Based on the prior art, the invention provides a sodium-free vanadium-phosphorus-oxygen catalyst and a preparation method thereof, the sodium-free vanadium-phosphorus-oxygen catalyst is used for selective oxidation of short-chain hydrocarbon, is particularly suitable for preparing maleic anhydride by oxidation of n-butane, and has improved physical properties and catalytic performance.
Through the preparation research of the sodium-free vanadium-phosphorus oxide catalyst, the inventor of the patent application finds that the catalytic performance is obviously improved when the sodium-free vanadium-phosphorus oxide catalyst is applied to the oxidation reaction of hydrocarbon by improving the preparation process and raw materials of the vanadium-phosphorus oxide catalyst. In particular to the oxidation reaction of n-butane, wherein the conversion activity of the n-butane is greatly improved to more than 94 percent, and the selectivity of the maleic anhydride is improved to more than 71 percent.
The invention provides a sodium-free vanadium phosphorus oxide catalyst, which is a sodium-free vanadium phosphorus oxide catalyst.
Further wherein the sodium free system vanadium phosphorus oxide catalyst comprises vanadium phosphorus oxide and a co-agent.
Further, the molar ratio of phosphorus to vanadium in the vanadium phosphorus oxide is 1.0 to 1.2, and vanadium and phosphorus in the vanadium phosphorus oxide are expressed as (VO)2P2O7And beta-VOPO4The vanadium oxide exists in a form, and the average valence of vanadium in the vanadium phosphorus oxide is 4.0-4.5.
Further, the active auxiliary agent is composed of molybdenum, bismuth or a mixture of the molybdenum and the bismuth, and the content of the active auxiliary agent is 0.1-10% of the weight of the catalyst; preferably 0.2-5%; most preferably 0.5 to 2%.
Further, the main raw materials of the sodium-free system vanadium-phosphorus-oxygen catalyst comprise a vanadium source and a phosphorus source.
Further wherein the phosphorus source comprises phosphoric acid, phosphorus pentoxide, or a phosphorus halide, preferably phosphoric acid; wherein the vanadium source comprises vanadium pentoxide, ammonium metavanadate, preferably vanadium pentoxide.
Further, the phosphoric acid is sodium-free phosphoric acid, or industrial-grade phosphoric acid is selected, wherein sodium ions can be removed by electrophoresis or semipermeable membrane dialysis, and the content of the sodium ions is required to be less than 5ppm, preferably 1-0 ppm; the vanadium pentoxide raw material is sodium-free vanadium pentoxide or industrial-grade vanadium pentoxide, wherein sodium ions can be removed in a washing or ion exchange mode, and the content of the sodium ions is required to be lower than 5ppm, preferably 1-0 ppm.
Further, the means for detecting the sodium ion content in the catalyst comprises Atomic Absorption Spectrometry (AAS), an elemental fluorescence method (XRF) and inductively coupled plasma emission spectrometry (ICP), wherein the sodium ion content is controlled to be less than 10ppm, preferably less than 9.5ppm, more preferably less than 5ppm, and most preferably 1-0 ppm.
The invention provides a preparation method of a sodium-free vanadium phosphorus oxygen catalyst, which comprises the steps of controlling the content of sodium ions in main raw materials to be lower than 5ppm, preferably 1-0 ppm, wherein the main raw materials comprise a vanadium source and a phosphorus source; the phosphorus source comprises phosphoric acid, phosphorus pentoxide, or a phosphorus halide, preferably phosphoric acid; wherein the vanadium source comprises vanadium pentoxide, ammonium metavanadate, preferably vanadium pentoxide.
Further, the phosphoric acid is sodium-free phosphoric acid, or industrial-grade phosphoric acid is selected, wherein sodium ions can be removed by electrophoresis or semipermeable membrane dialysis, and the content of the sodium ions is required to be less than 5ppm, preferably 1-0 ppm; the vanadium pentoxide raw material is sodium-free vanadium pentoxide or industrial-grade vanadium pentoxide, wherein sodium ions can be removed in a washing or ion exchange mode, and the content of the sodium ions is required to be lower than 5ppm, preferably 1-0 ppm.
The invention also provides a preparation method of the sodium-free vanadium phosphorus oxygen catalyst, which comprises the steps of treating the catalyst or a catalyst precursor, wherein the catalyst precursor is preferably treated; the treatment process is to treat the catalyst precursor by adopting an organic solvent with higher solubility to sodium ions, and the treatment process is carried out in a heating and stirring environment; the solid-liquid volume ratio is 1: 2-20, preferably 1: 5-20, and most preferably 1: 10-20; the treatment temperature varies according to the boiling point of the organic solvent, and is required to be 30-300 ℃, preferably 20-30 ℃ below the boiling point of the organic solvent, and most preferably 10-15 ℃ below the boiling point of the organic solvent; the stirring speed is required to be 50-500 rpm, preferably 100-400 rpm, and most preferably 200-300 rpm; the treatment time is 1-20 h, preferably 2-10 h, and most preferably 3-5 h.
Further, the organic solvent is dichloromethane, tetrahydrofuran, ethylene glycol, glycerol, dimethyl sulfoxide, preferably ethylene glycol, glycerol, most preferably ethylene glycol.
The sodium-free vanadium phosphorus oxygen catalyst is suitable for heterogeneous selective oxidation of short-chain alkane.
The sodium-free vanadium-phosphorus-oxygen catalyst is particularly suitable for preparing maleic anhydride by gas-phase oxidation of n-butane.
The sodium-free vanadium phosphorus oxide catalyst is characterized in that vanadium phosphorus oxide is basically (VO)2P2O7And beta-VOPO4The form exists. The term "substantially" means (VO)2P2O7And beta-VOPO4The form accounts for more than 90 percent of the total weight of the vanadium phosphorus oxide.
Synthesis of vanadium phosphorus oxide:
the synthesis of vanadium phosphorus oxide may be carried out in a conventional manner. The synthesis is divided into three stages, namely a first stage, reduction of the high-valence vanadium compound in a reducing solvent. The high-valence vanadium compound as a vanadium source is preferably sodium-free vanadium pentoxide, wherein the content of sodium ions is less than 5ppm, preferably 1-0 ppm; as reducing solvent, aliphatic or aromatic alcohols or mixtures thereof are preferred, for example: isobutanol and benzyl alcohol. During the period, along with the introduction of phosphorus element, as a phosphorus source, sodium-free phosphoric acid is preferred, wherein the content of sodium ions is less than 5ppm, preferably 1-0 ppm. And cooling the reacted slurry to room temperature, carrying out suction filtration, washing with an organic solvent, drying after washing, and roasting to obtain the VPO catalyst precursor. The second stage, the molding stage. In one embodiment, the sodium free vanadium phosphorus oxide catalyst is configured as a shaped body suitable for a fixed bed reactor. For this purpose, the sodium-free catalysts of the invention can be compacted by means of equipment familiar to those skilled in the art, such as tablet presses or extruders, and subsequently calcined to give stable shaped bodies. Possible shaped bodies are spheres, trilobes, cylinders, hollow cylinders, raschig rings or spoke rings, etc. And a third stage, activating the catalyst. The catalyst activation can be selected from reactive atmosphere activation, i.e. activation in an n-butane and air atmosphere, and non-reactive atmosphere activation, i.e. activation in an air, inert gas and water vapor atmosphere. The activation process is a process familiar to those skilled in the art and is not limited by this patent.
Before or after recovering the catalyst precursor, molybdenum, bismuth or a mixture of the two may be added during the preparation of the catalyst precursor to obtain a VPO catalyst containing a co-agent. The molybdenum and bismuth may be in the form of molybdenum and bismuth-containing monomers or compounds, such as metals, oxides, hydroxides, carbonates, nitrates, or the like.
Compared with the prior art, the sodium-free vanadium phosphorus oxide catalyst has the following characteristics:
the oxidation of n-butane to prepare maleic anhydride belongs to lattice oxygen oxidation reaction, and in the oxidation reaction process, the oxygen molecules adsorbed on the surface of the catalyst receive V4+Electron formation in species O2-And O-Lattice oxygen ion, lattice oxygen ion O2-Is a nucleophile which intercalates through nucleophilic additionTo the point where the hydrocarbon molecule is electron deficient, resulting in selective oxidation. And the surface V of sodium ions and vanadium phosphorus oxide in the catalyst4+The combination of species has a large influence on the oxidation process. First, sodium ions and vanadium phosphorus oxide surface V4+The combination of species, affecting the lattice oxygen ion O2-Reducing the oxygen content of crystal lattices on the surface of the catalyst, thereby influencing the activity of the catalyst; secondly, combined with sodium ions V4+The occurrence of species distorts the local charge density and the acidity of the active center, and influences the intermediate state structure formed between the n-butane molecule and the active center on the surface of vanadium phosphorus oxide, and the structure directly determines the type of the final product, so the existence of sodium ions has a great influence on the selectivity of the catalyst.
The sodium-free vanadium phosphorus oxide catalyst of the invention better overcomes the problems. Tests show that the activity and selectivity of the original catalyst are obviously improved on the basis of the original catalyst by the invention of the sodium-free vanadium-phosphorus-oxygen catalyst.
Detailed Description
The contents of the present patent are further illustrated below by the following examples, but the present patent is not limited to these examples.
Example 1
Weighing 19g of sodium-free type V2O5Adding powder (the content of sodium ions is 5-0 ppm) into a three-neck flask, adding 200mL of isobutanol and 50mL of benzyl alcohol, heating to reflux at a specific stirring rate, refluxing for 6h, cooling to 80 ℃, slowly dropwise adding 27.6g of 100 wt% industrial-grade phosphoric acid, heating to reflux, reacting for 6h, and naturally cooling. And (3) after the temperature of the slurry is reduced to room temperature, carrying out suction filtration, washing with isobutanol, drying for 5h at 120 ℃, and then roasting for 5h at 260 ℃ to obtain the VPO catalyst precursor. Adding 3% of graphite into the obtained precursor powder, uniformly mixing, tabletting and forming, then placing in an atmosphere oven for activation, controlling the activation atmosphere to be air/water vapor/nitrogen at 50%/25%/25%, heating to 430 ℃ at the heating rate of 3 ℃/min, and keeping at 430 ℃ for 6h to obtain the VPO catalyst finished product.
Taking VPO catalyst3mL, diluted with quartz sand of the same mesh number at a dilution ratio of 1:3 (catalyst/quartz sand), placed in a fixed bed reactor with an inner diameter of 15mm, and subjected to catalyst performance evaluation. The composition of the raw material gas for reaction is 1.5 percent of n-butane and 98.5 percent of air, and the volume space velocity is 2000h-1And the reaction temperature was 430 ℃.
Example 2
Weighing 19g of technical grade V2O5Adding powder into a three-neck flask, adding 200mL of isobutanol and 50mL of benzyl alcohol, heating to reflux at a specific stirring rate, refluxing for 6h, cooling to 80 ℃, slowly dropwise adding 27.6g (5-0 ppm of sodium ion content) of 100 wt% sodium-free phosphoric acid, heating to reflux, reacting for 6h, and naturally cooling. And (3) after the temperature of the slurry is reduced to room temperature, carrying out suction filtration, washing with isobutanol, drying for 5h at 120 ℃, and then roasting for 5h at 260 ℃ to obtain the VPO catalyst precursor. Adding 3% of graphite into the obtained precursor powder, uniformly mixing, tabletting and forming, then placing in an atmosphere oven for activation, controlling the activation atmosphere to be air/water vapor/nitrogen at 50%/25%/25%, heating to 430 ℃ at the heating rate of 3 ℃/min, and keeping at 430 ℃ for 6h to obtain the VPO catalyst finished product.
The VPO catalyst 3mL is diluted by quartz sand with the same mesh number, the dilution ratio is 1:3 (catalyst/quartz sand), and the catalyst is placed in a fixed bed reactor with the inner diameter of 15mm for performance evaluation. The composition of the raw material gas for reaction is 1.5 percent of n-butane and 98.5 percent of air, and the volume space velocity is 2000h-1And the reaction temperature was 430 ℃.
Example 3
Weighing 19g of sodium-free type V2O5Adding powder (5-0 ppm of sodium ion content), adding 200mL of isobutanol and 50mL of benzyl alcohol into a three-neck flask, heating to reflux at a specific stirring rate, refluxing for 6h, cooling to 80 ℃, slowly dropwise adding 27.6g (5-0 ppm of sodium ion content) of 100 wt% sodium-free phosphoric acid, heating to reflux, reacting for 6h, and naturally cooling. And (3) after the temperature of the slurry is reduced to room temperature, carrying out suction filtration, washing with isobutanol, drying for 5h at 120 ℃, and then roasting for 5h at 260 ℃ to obtain the VPO catalyst precursor. Adding 3% graphite into the obtained precursor powder, mixing uniformly, and tabletting for moldingAnd then placing the catalyst in an atmosphere oven for activation, controlling the activation atmosphere to be air/water vapor/nitrogen at 50%/25%/25%, raising the temperature to 430 ℃ at the rate of 3 ℃/min, and keeping the temperature at 430 ℃ for 6 hours to obtain a VPO catalyst finished product.
The VPO catalyst 3mL is diluted by quartz sand with the same mesh number, the dilution ratio is 1:3 (catalyst/quartz sand), and the catalyst is placed in a fixed bed reactor with the inner diameter of 15mm for performance evaluation. The composition of the raw material gas for reaction is 1.5 percent of n-butane and 98.5 percent of air, and the volume space velocity is 2000h-1And the reaction temperature was 430 ℃.
Example 4
Weighing 19g of technical grade V2O5Adding the powder into a three-neck flask, adding 200mL of isobutanol and 50mL of benzyl alcohol, heating to reflux at a specific stirring rate, refluxing for 6h, cooling to 80 ℃, slowly dropwise adding 27.6g of 100 wt% industrial-grade phosphoric acid, heating to reflux, reacting for 6h, and naturally cooling. And after the temperature of the slurry is reduced to room temperature, carrying out suction filtration, washing with isobutanol, and drying for 5 hours at the temperature of 120 ℃.
Placing the obtained precursor in ethylene glycol, and treating under a heating and stirring environment, wherein the solid-liquid volume ratio is controlled to be 1: 15; the treatment temperature is 180 ℃, the stirring speed is 200 rpm, and the treatment time is 4 hours. And after the treatment is finished, carrying out suction filtration after the temperature of the slurry is reduced to room temperature, drying for 2h at 120 ℃, and then roasting for 5h at 260 ℃ to obtain the treated VPO catalyst precursor.
Adding 3% of graphite into the treated precursor powder, uniformly mixing, tabletting and forming, then placing in an atmosphere oven for activation, controlling the activation atmosphere to be air/water vapor/nitrogen at 50%/25%/25%, heating to 430 ℃ at the heating rate of 3 ℃/min, and keeping at 430 ℃ for 6h to obtain the VPO catalyst finished product.
The VPO catalyst 3mL is diluted by quartz sand with the same mesh number, the dilution ratio is 1:3 (catalyst/quartz sand), and the catalyst is placed in a fixed bed reactor with the inner diameter of 15mm for performance evaluation. The composition of the raw material gas for reaction is 1.5 percent of n-butane and 98.5 percent of air, and the volume space velocity is 2000h-1And the reaction temperature was 430 ℃.
Example 5
Weighing 19g of sodium-free type V2O5Adding powder (5-0 ppm of sodium ion content), adding 200mL of isobutanol and 50mL of benzyl alcohol into a three-neck flask, heating to reflux at a specific stirring rate, refluxing for 6h, cooling to 80 ℃, slowly dropwise adding 27.6g (5-0 ppm of sodium ion content) of 100 wt% sodium-free phosphoric acid, heating to reflux, reacting for 6h, and naturally cooling. And after the temperature of the slurry is reduced to room temperature, carrying out suction filtration, washing with isobutanol, and drying for 5 hours at the temperature of 120 ℃.
Placing the obtained precursor in ethylene glycol, and treating under a heating and stirring environment, wherein the solid-liquid volume ratio is controlled to be 1: 20; the treatment temperature was 185 ℃, the stirring rate was 250 rpm, and the treatment time was 5 hours. And after the treatment is finished, carrying out suction filtration after the temperature of the slurry is reduced to room temperature, drying for 2h at 120 ℃, and then roasting for 5h at 260 ℃ to obtain the treated VPO catalyst precursor.
Adding 3% of graphite into the treated precursor powder, uniformly mixing, tabletting and forming, then placing in an atmosphere oven for activation, controlling the activation atmosphere to be air/water vapor/nitrogen at 50%/25%/25%, heating to 430 ℃ at the heating rate of 3 ℃/min, and keeping at 430 ℃ for 6h to obtain the VPO catalyst finished product.
The VPO catalyst 3mL is diluted by quartz sand with the same mesh number, the dilution ratio is 1:3 (catalyst/quartz sand), and the catalyst is placed in a fixed bed reactor with the inner diameter of 15mm for performance evaluation. The composition of the raw material gas for reaction is 1.5 percent of n-butane and 98.5 percent of air, and the volume space velocity is 2000h-1And the reaction temperature was 430 ℃.
Comparative example 1
Weighing 19g of technical grade V2O5Adding the powder into a three-neck flask, adding 200mL of isobutanol and 50mL of benzyl alcohol, heating to reflux at a specific stirring rate, refluxing for 6h, cooling to 80 ℃, slowly dropwise adding 27.6g of 100 wt% industrial-grade phosphoric acid, heating to reflux, reacting for 6h, and naturally cooling. And (3) after the temperature of the slurry is reduced to room temperature, carrying out suction filtration, washing with isobutanol, drying for 5h at 120 ℃, and then roasting for 5h at 260 ℃ to obtain the VPO catalyst precursor. Adding 3% of graphite into the obtained precursor powder and mixingAnd (3) uniformly tabletting and forming, then placing the obtained product into an atmosphere oven for activation, controlling the activation atmosphere to be air/water vapor/nitrogen at 50%/25%/25%, heating the obtained product to 430 ℃ at the heating rate of 3 ℃/min, and keeping the obtained product at the temperature of 430 ℃ for 6 hours to obtain a VPO catalyst finished product.
The VPO catalyst 3mL is diluted by quartz sand with the same mesh number, the dilution ratio is 1:3 (catalyst/quartz sand), and the catalyst is placed in a fixed bed reactor with the inner diameter of 15mm for performance evaluation. The composition of the raw material gas for reaction is 1.5 percent of n-butane and 98.5 percent of air, and the volume space velocity is 2000h-1And the reaction temperature was 430 ℃.
TABLE 1
Compared with the prior art, the sodium-free vanadium phosphorus oxide catalyst is obtained by improving the aspects of local substance composition and local trace element influence on the surface of the vanadium phosphorus oxide catalyst. So that the surface V of the vanadium phosphorus oxide4+The species are exposed more thoroughly, and the oxygen ions O in the crystal lattice2-The production rate is higher, so that the catalyst activity is higher; in addition, the sodium-free environment of the vanadium phosphorus oxide surface makes V4+The local charge density and the acidity of the active center of the species are more stable, and the target phase state intermediate structure formed between the n-butane molecule and the active center is more single, so that the selectivity of the catalyst is higher. From the application result, the n-butane conversion activity of the sodium-free vanadium phosphorus oxide catalyst is greatly improved to more than 94%, and the selectivity of maleic anhydride is improved to more than 71%; and the stability of different batches of reactions is better.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (16)
1. Sodium-free vanadium-phosphorus-oxygen catalystThe method is characterized in that the catalyst is a sodium-free system vanadium phosphorus oxide catalyst; the main raw materials of the sodium-free system vanadium-phosphorus-oxygen catalyst comprise a vanadium source and a phosphorus source; the content of sodium ions in the main raw material is lower than 5 ppm; the content of sodium ions in the catalyst is controlled to be below 5 ppm; the sodium-free system vanadium-phosphorus-oxygen catalyst comprises vanadium-phosphorus oxide and a coagent; the molar ratio of phosphorus to vanadium in the vanadium phosphorus oxide is 1.0-1.2, and vanadium and phosphorus in the vanadium phosphorus oxide are (VO)2P2O7And beta-VOPO4The form exists.
2. The catalyst according to claim 1, wherein the average valence of vanadium in the vanadium phosphorus oxide is 4.0 to 4.5.
3. The catalyst of claim 1, wherein the co-agent is selected from the group consisting of molybdenum, bismuth, and mixtures thereof, and is present in an amount of 0.1 to 10% by weight of the catalyst.
4. The catalyst of claim 3 wherein the coagent is present in an amount of 0.2 to 5% by weight of the catalyst.
5. The catalyst of claim 1, wherein the phosphorus source comprises phosphoric acid, phosphorus pentoxide, or a phosphorus halide; wherein the vanadium source comprises vanadium pentoxide and ammonium metavanadate.
6. The catalyst of claim 5, wherein the phosphoric acid is sodium-free or alternatively technical grade phosphoric acid, wherein sodium ions can be removed by electrophoresis or semipermeable membrane dialysis, and the sodium ion content is required to be less than 5 ppm; the vanadium pentoxide raw material is sodium-free vanadium pentoxide or industrial-grade vanadium pentoxide, wherein sodium ions can be removed by washing or ion exchange, and the content of the sodium ions is required to be lower than 5 ppm.
7. The catalyst according to claim 6, wherein the sodium ion content of the phosphoric acid is 1-0 ppm; the content of sodium ions in the vanadium pentoxide is 1-0 ppm.
8. The catalyst according to claim 1, wherein the sodium ion content detection means in the catalyst comprises Atomic Absorption Spectrometry (AAS), elemental fluorescence (XRF) and inductively coupled plasma emission spectrometry (ICP), and the sodium ion content is controlled to be 1-0 ppm.
9. The method for preparing the sodium-free vanadium phosphorus oxide catalyst according to claim 1, comprising controlling the content of sodium ions in the main raw materials to be less than 5ppm, wherein the main raw materials comprise a vanadium source and a phosphorus source; the phosphorus source comprises phosphoric acid, phosphorus pentoxide, or a phosphorus halide; wherein the vanadium source comprises vanadium pentoxide and ammonium metavanadate.
10. The method according to claim 9, wherein the content of sodium ions in the main raw material is controlled to be 1 to 0 ppm.
11. The process of claim 9, wherein the phosphoric acid is sodium-free or alternatively technical grade phosphoric acid, wherein sodium ions are removed by electrophoresis or by semipermeable membrane dialysis, requiring a sodium ion content of less than 5 ppm; the vanadium pentoxide raw material is sodium-free vanadium pentoxide or industrial-grade vanadium pentoxide, wherein sodium ions can be removed by washing or ion exchange, and the content of the sodium ions is required to be lower than 5 ppm.
12. A method for preparing the sodium-free vanadium phosphorus oxide catalyst according to claim 1, comprising treating the catalyst or a catalyst precursor; the treatment process is to treat the catalyst precursor by adopting an organic solvent with higher solubility to sodium ions, and the treatment process is carried out in a heating and stirring environment; the solid-liquid volume ratio is required to be 1: 2-20; the treatment temperature is changed according to different boiling points of the organic solvent, and is required to be 30-300 ℃; the stirring speed is required to be 50-500 rpm; the treatment time is 1-20 h.
13. The preparation method according to claim 12, wherein the solid-liquid volume ratio is 1: 10-20; the treatment temperature is changed according to different boiling points of the organic solvent, and is required to be 20-30 ℃ below the boiling point of the organic solvent; the stirring speed is required to be 100-400 rpm; the treatment time is 2-10 h.
14. The method according to claim 12, wherein the organic solvent is dichloromethane, tetrahydrofuran, ethylene glycol, glycerol, or dimethyl sulfoxide.
15. Use of a sodium-free vanadium phosphorus oxide catalyst according to any one of claims 1 to 8 or a catalyst prepared by the preparation method according to any one of claims 9 to 14 for the heterogeneous selective oxidation of short-chain alkanes.
16. The use according to claim 15, wherein the sodium-free vanadium phosphorus oxide catalyst is suitable for the gas phase oxidation of n-butane to maleic anhydride.
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| CN1091998A (en) * | 1992-12-08 | 1994-09-14 | 孟山都公司 | Be used to prepare the catalyst of the promoter elements that contains vanadium-phosphorus oxide and selection of maleic anhydride |
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