CN1251799C - Vanadium phosphorus oxygen catalyst for preparing acrylic acid and acetic acid by oxidation of propane and preparation method thereof - Google Patents
Vanadium phosphorus oxygen catalyst for preparing acrylic acid and acetic acid by oxidation of propane and preparation method thereof Download PDFInfo
- Publication number
- CN1251799C CN1251799C CN200410013902.5A CN200410013902A CN1251799C CN 1251799 C CN1251799 C CN 1251799C CN 200410013902 A CN200410013902 A CN 200410013902A CN 1251799 C CN1251799 C CN 1251799C
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- catalyst
- vanadium
- propane
- isobutanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000001294 propane Substances 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title abstract description 38
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 title 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- -1 vanadyl pyrophosphate Chemical compound 0.000 claims abstract description 7
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 21
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 235000012736 patent blue V Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 229940035429 isobutyl alcohol Drugs 0.000 abstract 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000013467 fragmentation Methods 0.000 description 4
- 238000006062 fragmentation reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- KJESGYZFVCIMDE-UHFFFAOYSA-N 1-chloroethanol Chemical compound CC(O)Cl KJESGYZFVCIMDE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WOFDVDFSGLBFAC-UHFFFAOYSA-N lactonitrile Chemical compound CC(O)C#N WOFDVDFSGLBFAC-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a VPO catalyst prepared from vanadium pentoxide and a phosphoric acid in mixed solvents of an isobutyl alcohol and a benzyl alcohol, and polyethylene glycol is used as a dispersing agent, wherein the atomic ratio of phosphorus to vanadium is 1 to 1. Specific surface area is as large as 70 to 78m<2>/g, and a main phase is a vanadyl pyrophosphate phase. The VPO catalyst is used as a catalyst for preparing an acrylic acid and an acetic acid by the air oxidation of propane, a single pass conversion rate is from 37 to 72% in a typical reaction temperature interval of 380 to 400 DEG C, selectivity to the acrylic acid is from 5 to 35%, and overall selectivity to the acrylic acid and the acetic acid is from 19 to 83%. Under optimum reaction conditions, the conversion rate of the propane is 40.3%, the selectivity to the acrylic acid is 33.8%, selectivity to the acetic acid is 49.4%, the yield of the acrylic acid is 13.6%, the overall yield of the two acids is 33.5%, and space time yield is much higher than that of the similar catalysts reported at present. The present invention discloses a preparation method of the catalyst.
Description
One, technical field
The present invention relates to vanadium-phosphor oxide catalyst and on this catalyst, prepare acrylic acid and acetate with air part propane oxide.
Two, technical background
Acrylic acid (Acrylic acid, be called for short AA) and ester class thereof are crucial Organic Chemicals, and its unsaturated double-bond autohemagglutination easily takes place or forms the macromolecular material of multiple different performance and purposes with other unsaturated hydrocarbons generation poly such as polyacrylate etc.They are widely used in industries such as coating, chemical fibre, weaving, light industry, and oil exploitation, oil dope etc.At present also continually developing the purposes that makes new advances.The production capacity of whole world acrylic acid and ester thereof grows steadily in recent years, nineteen ninety-five acrylic acid and the output of ester be respectively 2,470,000 tons and 177～2,040,000 tons, global acrylic acid production capacity was 3,240,000 tons in 2000, acrylate production capacity is 2,650,000 tons, and this growth will continue to keep in the expected time.
A plurality of developing stage have been passed through in acrylic acid production.Josepl Redtenbach in 1843 has obtained acrylic acid by acrolein oxidation in the presence of silver oxide.Offo Rohm in 1901 finds that the polymer of acrylic acid and ester thereof has important industrial use, and so far acrylic acid and ester thereof get more and more people's extensive concerning.Nineteen twenty-seven Rohm ﹠amp; Haas company is that raw material makes cyanoethanol with chlorethanol and Cymag, makes methyl acrylate through dehydration, hydrolysis and methanol esterification again, thereby has begun suitability for industrialized production.At present acrylic acid main production method is the propylene two-step oxidizing process, and the 85%[that accounts for the acrylic acid total output is referring to Yang Xiangui etc., gas chemical industry, 1998,23 (4): 43-47].
Acetate is a kind of important basic organic acid raw material.Be mainly used in and produce vinyl acetate, and be used to make fiber, paint, adhesive, copolymer resin etc.It also is widely used in and makes aceticanhydride, monoxone, various acetate, ketene dimer, dredges guanidine-acetic acid, acetonitrile, acetyl arylamine, and then is used to produce acetate fiber, plasticizer, agricultural chemicals, medicine, seven material, spices etc.The synthesis technique of acetate mainly contains acetaldehyde oxidation, and methanol carbonyl synthetic method and some are being developed but still preindustrial new method, as synthesis gas direct synthesis technique, direct oxidation of ethylene to method etc.
Along with the minimizing gradually of petroleum resources and a large amount of development and use of natural gas resource, making important organic chemicals by the low-carbon alkanes direct oxidation of relative low price becomes the tempting production method of prospect.Because the normal butane selective oxidation is produced the maleic anhydride process route and obtained immense success, so people's expectation also can be produced organic chemicals such as acrylic acid by the propane direct oxidation.Propane is the key component in casing-head gas, natural gas, the refinery gas, and the source is abundant, and price is cheap than propylene, simultaneously because the simplification of process route, the reduction of energy consumption etc. all will bring huge economic benefit, and environmental friendliness more.Preparing acrylic acid by the propane direct oxidation has had some basic research reports, and catalyst mainly concentrates on vanadium-phosphor oxide catalyst (VPOs), heteropoly acid and salt (HPCs) thereof and composite metal oxide catalyst systems such as (MMOs).Adopt Cs as Noritaka, Miznno etc.
2.5Fe
0.08H
1.26PVMo
11O
40Catalyst, 380 ℃ of reaction temperatures, conversion of propane 47%, acrylic acid yield 13%[is referring to J.Mole.Catal.A:Chem., and 1996,114:309-317].PMo heteropoly acid (the H that Wataru Ueda adopts pyridine to handle
3PMo
12O
40) make catalyst, 380 ℃ of reaction temperatures, when conversion of propane 12%, acrylic acid selectivity 24%, acetic acid selectivity 15%[is referring to Appl.Catal.A:Gen., and 1999,182:357-363].Realized 42% AA yield on the Mo-V-Te-Nb-O catalyst of M.M.Lin report, but its reaction gas consists of C
3H
8/ Air/H
2O (g)=1/96/3, wherein the content of propane is very low, the space-time yield of catalyst and efficient all quite low [referring to Appl.Catal.A:Gen., 2003,250:305-318].Domestic also have research to the direct acrylic acid synthesizing of propane, adopt Vanadyl pyrophosphate to make catalyst as people such as Zhao of Zhejiang University such as pines, when 385 ℃ of reaction temperatures, obtain conversion of propane 37%, acrylic acid selectivity 39%, acrylic acid once through yield 14.4%, but same problem is the very low (C of content of propane in the reaction gas
3H
8/ O
2/ H
2O (g)=1/24/40/40), catalyst efficiency relatively poor [referring to " petrochemical industry ", 1995,24:157-160].During by propane partial oxidation system acrylic acid, a spot of by-product acetic acid is arranged generally.Generate acrylic acid and acetate if can realize highly selective in this oxidation step process, then have important application, this has constituted the important foundation of patent application of the present invention, and the research of this respect is still blank at present basically.On the whole, acrylic acid of China and acetate existing manufacturing technique technology are also relatively backward, small scale, yield poorly, and corresponding research work also seldom.Along with the fast-developing of Chinese national economy and to the increase day by day of acrylic acid, acetate and esters product demand thereof, the production technology that change to fall behind is imperative, and it is significant therefore to strengthen the basic research of this respect and technological achievement that exploitation has independent intellectual property right.
In above-mentioned three kinds of catalyst, vanadium-phosphor oxide catalyst (hereinafter to be referred as vpo catalyst) is one of catalyst that has very much application prospect, in the production route of normal butane selective oxidation preparing maleic anhydride (MA), obtained success at present, it is generally 60～70% to the MA selectivity, MA yield 55～58%.Yet when VPOs was applied to the selective oxidation of propane, especially space-time yield was generally lower for the acrylic acid yield that obtains at present.Be reported on the vpo catalyst that adds 0.01%Ce as Cheng Hua etc. and realized 18.8% acrylic acid yield, this is the highest acrylic acid yield of reporting on the present vpo catalyst, but reaction gas propane content only is 3.2% in the operation parameter, [referring to " petrochemical industry ", 1999,12:8.3-807], so the space-time yield of catalyst and actual catalytic efficiency are still on the low side.More further be oxidized to oxycarbide at such catalyst top oxidation product.The catalytic performance of vpo catalyst and its preparation history are closely related, and the factor that influences its performance is more.P/V is than the key factor that is the decision catalyst performance, because the crystal phase structure of its decision catalyst.The general vpo catalyst for preparing in organic media has more single, that activity is higher crystalline phase and bigger specific area than the catalyst of aqueous phase preparation.Different drying conditions and activation phenomenon also can exert an influence to crystalline phase and specific area.It is generally acknowledged the Vanadyl pyrophosphate phase [(VO)
2P
2O
7] be its main active phase, V
4+It is main active specy; With VOPO
4The V that form exists
5+Help improving acrylic acid selectivity, and excessive V
5+The complete oxidation that will cause product, but to V
5+Definite effect remain at present the dispute.The introducing of auxiliary agent may change the crystal phase structure of catalyst, but little to the valence state influence of surperficial V ion.The factor that influences the acrylic acid yield respond temperature, unstripped gas composition etc.The general optimal reaction temperature interval that exists.High as a rule O
2/ C
3Than the raising that helps acrylic acid yield, and acrylic acid productive rate and selectivity all descend with the raising of propane content in the reaction gas.Introduce a certain amount of steam in the reaction gas and help improving acrylic acid selectivity, this may be because having of steam is beneficial to product from the catalyst surface desorption, has avoided over oxidation.
Three, summary of the invention
The objective of the invention is to develop a kind of vpo catalyst that the propane highly selective can be oxidized to acrylic acid and acetate and have greater catalytic efficient.
Technical scheme of the present invention is as follows:
A kind of oxidation of propane prepares the vanadium-phosphor oxide catalyst of acrylic acid and acetate, and it prepares in isobutanol-phenmethylol mixed solvent with vanadic anhydride and phosphoric acid, is dispersant with the polyethylene glycol, and wherein phosphorus atoms number/vanadium atom number is 1.1, and specific area is 70-78m
2/ g, its main thing are the Vanadyl pyrophosphate phase mutually.
The preparation of vanadium-phosphor oxide catalyst of the present invention is made up of the following step:
1. vanadic anhydride is mixed with isobutanol-phenmethylol mixed solvent, add hot reflux 4-6 hour, isobutanol-phenmethylol mixed solvent is that the phenmethylol by the isobutanol of 1-1.2 part volume and 1 part of volume mixes, the consumption of vanadic anhydride and isobutanol-phenmethylol mixed solvent is 1 gram vanadic anhydride solubilizer 22-32ml
2. the adding polyethylene glycol continues backflow 0.5-2 hour, and the amount of the polyethylene glycol of adding and the mass ratio of vanadic anhydride are 0.35-0.71: 1,
3. adding phosphoric acid, the addition of phosphoric acid are that to make phosphorus atoms number/vanadium atom number be 1.2, and the phosphoric acid of adding can be the phosphoric acid of 85% (m/m),
4. continue backflow 5-6 hour, have sky-blue to blue look precipitation to separate out gradually,
5. reactant liquor is cooled to room temperature, left standstill 5-10 hour, filter, respectively for several times with isobutanol, acetone washing,
6. filtrate is warming up to 100-120 ℃ of drying in air atmosphere, promptly gets vanadium-phosphor oxide catalyst precursor of the present invention.
7. under 400 ℃, in nitrogen atmosphere, activate 6 hours in activation 2 hours, the reaction mixture gas before using, get fresh vanadium-phosphor oxide catalyst of the present invention.
The molecular weight polyethylene glycol that adds in the above-mentioned steps 2 is 6,000-20,000.
The purposes of vanadium-phosphor oxide catalyst of the present invention is the catalyst for preparing acrylic acid and acetate as air oxidation propane.The specific area of vanadium-phosphor oxide catalyst of the present invention is up to 70-78m
2/ g, the main crystalline phase of catalyst is the Vanadyl pyrophosphate phase, scanning electron microscopic observation is found that the vanadium phosphorus oxide particle is less and is distributed relatively evenly (see figure 1).The Preparation of catalysts method is simple, suitable batch production.When being applied to propane air oxidation system acrylic acid and acetate, in 380-400 ℃ representative temperature interval, its conversion per pass is 37-72%, is 5-35% to the acrylic acid selectivity, is 19-83% to the overall selectivity of acrylic acid and acetate.Conversion of propane is 40.3% under the optimum reaction condition, and the acrylic acid selectivity is 33.8%, and acetic acid selectivity is 49.4%, and the acrylic acid yield is that 13.6%, two sour total recovery is 33.5%.
Characteristics of the present invention are: 1. add a certain amount of polyethylene glycol as dispersant in the Preparation of catalysts process, make catalyst particle little and distribute more evenly, reduced V simultaneously
5+The content of species.2. by the adding mode of control phosphoric acid, the specific area and the catalyst that have increased catalyst extremely significantly have unique configuration of surface.3. under optimized reaction conditions, catalyst still can keep very high acrylic acid, acetate diacid overall selectivity when having higher conversion of propane, and other accessory substance is considerably less.
Four, description of drawings
Fig. 1 is the transmission electron microscope photo (amplifying 50,000 times) of catalyst.
Five, the specific embodiment
Embodiment 1
Take by weighing V
2O
52.5 gram places isobutanol/phenmethylol (40ml/35ml) mixed liquor, 140 ℃ of backflows are after 6 hours, the adding molecular weight is 6000 polyethylene glycol 1.4 grams, continue to reflux 1 hour, press the atomic ratio of P/V=1.2/1, the mode that employing drips adds 85% phosphoric acid 2.25ml.Continue to reflux 5 hours.Filtration, drying, the De Lanse sediment.Sediment is dry in 120 ℃ of air atmospheres, get catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.5MP pressure, fragmentation, sieve is got 20-40 order sample particle and activate 2 hours in nitrogen atmosphere under 400 ℃, switches to reaction atmosphere (C again
3H
8/ O
2/ He=17/30/53) the middle continuation activates 6 hours, and the fresh catalyst that obtains activating, catalyst specific surface are 78m
2/ g, the P/V atomic ratio of ICP testing result show sample is 1.10.Take by weighing activated fresh catalyst 1 gram, place in the U-shaped crystal reaction tube of internal diameter 0.8cm and carry out the catalytic perfomance evaluation.In reaction temperature is 400 ℃, and air speed is 900h
-1, unstripped gas consists of C
3H
8/ O
2React under the condition of/He=17/30/53 (V/V), reaction mixture gas is through online gas chromatographic analysis, and its conversion of propane is 52.9%, and the acrylic acid selectivity is 5.4%, and the acetic acid selectivity is 15.7%, and the acrylic acid yield is that 2.9%, two sour total recovery is 11.2%.
Embodiment 2
Take by weighing V
2O
53.0 gram places isobutanol/phenmethylol (48ml/48ml) mixed liquor, 140 ℃ of backflows are after 4 hours, the adding molecular weight is 10,000 polyethylene glycol 2.1 grams, continues to reflux 2 hours, press the atomic ratio of P/V=1.2/1, the mode that employing drips adds 85% phosphoric acid 2.70ml.Continue to reflux 6 hours.Filtration, drying, the De Lanse sediment.Sediment is dry in 100 ℃ of air atmospheres, get catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.5MP pressure, fragmentation, sieve is got 20-40 order sample particle and activate 2 hours in nitrogen atmosphere under 400 ℃, switches to reaction atmosphere (C again
3H
8/ O
2/ He=17/30/53) the middle continuation activates 6 hours, and the fresh catalyst that obtains activating, catalyst specific surface are 72m
2/ g, the P/V atomic ratio of ICP testing result show sample is 1.08.Take by weighing activated fresh catalyst 1 gram, place in the U-shaped crystal reaction tube of internal diameter 0.8cm and carry out the catalytic perfomance evaluation.In reaction temperature is 380 ℃, and air speed is 900h
-1, unstripped gas consists of C
3H
8/ O
2/ He/H
2React under the condition of O=13.6/24/42.4/20 (V/V), reaction mixture gas is through online gas chromatographic analysis, and its conversion of propane is 50.4%, the acrylic acid selectivity is 16.4%, the acetic acid selectivity is 29.4%, and the acrylic acid yield is that 8.3%, two sour total recovery is 23.1%.
Embodiment 3
Take by weighing V
2O
53.2 gram places isobutanol/phenmethylol (35ml/35ml) mixed liquor, 140 ℃ of backflows are after 6 hours, the adding molecular weight is 6000 polyethylene glycol 1.5 grams, continue to reflux 1 hour, press the atomic ratio of P/V=1.2/1, the mode that employing drips adds 85% phosphoric acid 2.88ml.Continue to reflux 6 hours.Filtration, drying, the De Lanse sediment.Sediment is dry in 120 ℃ of air atmospheres, get catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.5MP pressure, fragmentation, sieve is got 20-40 order sample particle and activate 2 hours in nitrogen atmosphere under 400 ℃, switches to reaction atmosphere (C again
3H
8/ O
2/ He=17/30/53) the middle continuation activates 6 hours, and the fresh catalyst that obtains activating, catalyst specific surface are 76m
2/ g, the P/V atomic ratio of ICP testing result show sample is 1.12.Take by weighing activated fresh catalyst 1 gram, place in the U-shaped crystal reaction tube of internal diameter 0.8cm and carry out the catalytic perfomance evaluation.In reaction temperature is 380 ℃, and air speed is 900h
-1, unstripped gas consists of C
3H
8/ O
2Under the reaction condition of/He=17/30/53 (V/V), reaction mixture gas is through online gas chromatographic analysis, and its conversion of propane is 49%, and the acrylic acid selectivity is 6.7%, and the acetic acid selectivity is 13%, and the acrylic acid yield is that 3.3%, two sour total recovery is 9.7%.
Embodiment 4
Method for preparing catalyst is with embodiment 3.Take by weighing activated fresh catalyst 1 gram, place in the U-shaped crystal reaction tube of internal diameter 0.8cm and carry out the catalytic perfomance evaluation.In reaction temperature is 380 ℃, and air speed is 900h
-1, unstripped gas consists of C
3H
8/ O
2/ He/H
2React under the condition of O=11.9/21/37.1/30 (V/V), reaction mixture gas is through online gas chromatographic analysis, and its conversion of propane is 40.3%, the acrylic acid selectivity is 33.8%, acetic acid selectivity is 49.4%, and the acrylic acid yield is that 13.6%, two sour total recovery is 33.5%.
Embodiment 5
Take by weighing V
2O
54.0 gram places isobutanol/phenmethylol (70ml/58ml) mixed liquor, 140 ℃ of backflows are after 6 hours, the adding molecular weight is 20,000 polyethylene glycol 2.8 grams, continues to reflux 1 hour, press the atomic ratio of P/V=1.2/1, the mode that employing drips adds 85% phosphoric acid 3.60ml.Continue to reflux 6 hours.Filtration, drying, the De Lanse sediment.Sediment is dry in 120 ℃ of air atmospheres, get catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.5MP pressure, fragmentation, sieve is got 20-40 order sample particle and activate 2 hours in nitrogen atmosphere under 400 ℃, switches to reaction atmosphere (C again
3H
8/ O
2/ He=17/30/53) the middle continuation activates 6 hours, and the fresh catalyst that obtains activating, catalyst specific surface are 70m
2/ g, the P/V atomic ratio of ICP testing result show sample is 1.06.Take by weighing activated fresh catalyst 1 gram, place in the U-shaped crystal reaction tube of internal diameter 0.8cm and carry out the catalytic perfomance evaluation.In reaction temperature is 380 ℃, and air speed is 900h
-1, unstripped gas consists of C
3H
8/ O
2/ He/H
2React under the condition of O=10.2/18/31.8/40 (V/V), reaction mixture gas is through online gas chromatographic analysis, and its conversion of propane is 37.2%, the acrylic acid selectivity is 35.1%, acetic acid selectivity is 43.3%, and the acrylic acid yield is that 13.1%, two sour total recovery is 29.1%.
Claims (3)
1. an oxidation of propane prepares the vanadium-phosphor oxide catalyst of acrylic acid and acetate, it is characterized in that: in isobutanol-phenmethylol mixed solvent, prepare with vanadic anhydride and phosphoric acid, with the polyethylene glycol is dispersant, and phosphorus atoms number/vanadium atom number is 1.1 in the vanadium-phosphor oxide catalyst, and specific area is 70-78m
2/ g, its main thing are the Vanadyl pyrophosphate phase mutually.
2. the preparation method of the described vanadium-phosphor oxide catalyst of claim 1 is characterized in that being made up of the following step:
(1) vanadic anhydride is mixed with isobutanol-phenmethylol mixed solvent, add hot reflux 4-6 hour, isobutanol-phenmethylol mixed solvent is that the phenmethylol by the isobutanol of 1-1.2 part volume and 1 part of volume mixes, the consumption of vanadic anhydride and isobutanol-phenmethylol mixed solvent is 1 gram vanadic anhydride solubilizer 22-32ml
(2) add polyethylene glycol, continue backflow 0.5-2 hour, the amount of the polyethylene glycol of adding and the mass ratio of vanadic anhydride are 0.35-0.71: 1,
(3) add phosphoric acid, the addition of phosphoric acid is that to make phosphorus atoms number/vanadium atom number be 1.2, and the phosphoric acid of adding is the phosphoric acid of 85%m/m,
(4) continue backflow 5-6 hour, have sky-blue to blue look precipitation to separate out gradually,
(5) reactant liquor is cooled to room temperature, left standstill 5-10 hour, filter, respectively for several times with isobutanol, acetone washing,
(6) filtrate is warming up to 100-120 ℃ of drying in air atmosphere, promptly gets the vanadium-phosphor oxide catalyst precursor,
(7) under 400 ℃, in nitrogen atmosphere, activate 6 hours in activation 2 hours, the reaction mixture gas before the use, get fresh vanadium-phosphor oxide catalyst.
3. method for preparing catalyst according to claim 2 is characterized in that: the molecular weight of the polyethylene glycol that adds in the step 2 is 6,000-20,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410013902.5A CN1251799C (en) | 2004-01-15 | 2004-01-15 | Vanadium phosphorus oxygen catalyst for preparing acrylic acid and acetic acid by oxidation of propane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410013902.5A CN1251799C (en) | 2004-01-15 | 2004-01-15 | Vanadium phosphorus oxygen catalyst for preparing acrylic acid and acetic acid by oxidation of propane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1557549A CN1557549A (en) | 2004-12-29 |
| CN1251799C true CN1251799C (en) | 2006-04-19 |
Family
ID=34351164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200410013902.5A Expired - Fee Related CN1251799C (en) | 2004-01-15 | 2004-01-15 | Vanadium phosphorus oxygen catalyst for preparing acrylic acid and acetic acid by oxidation of propane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1251799C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157048B (en) * | 2007-11-20 | 2010-04-07 | 吐哈石油勘探开发指挥部石油天然气化工厂 | A high performance vanadium phosphorus oxygen catalyst with nanostructure as well as its preparing method |
| CN102151583B (en) * | 2011-02-21 | 2013-02-20 | 中国化学赛鼎宁波工程有限公司 | Method for preparing vanadium phosphate catalyst used in reaction of acrylic acid synthesized by acetic acid and formaldehyde |
| CN103801349B (en) * | 2014-03-19 | 2016-04-27 | 南京大学 | A kind of vpo catalyst and the application in dehydrating glycerin preparing propone aldehyde thereof |
| CN105363431B (en) * | 2014-08-29 | 2018-03-16 | 中国科学院大连化学物理研究所 | A kind of high activity [001] crystal face exposure ratio Mo V Te Nb O catalyst and its preparation and application |
| CN106248845B (en) * | 2015-06-10 | 2018-05-04 | 中国石油天然气股份有限公司 | Method for measuring content of unsaturated aldehyde in liquid phase mixture |
-
2004
- 2004-01-15 CN CN200410013902.5A patent/CN1251799C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1557549A (en) | 2004-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ciriminna et al. | One‐pot homogeneous and heterogeneous oxidation of glycerol to ketomalonic acid mediated by TEMPO | |
| CN103816930B (en) | A kind of vpo catalyst and the application in acetic acid (ester) and formaldehyde react acrylic acid processed (ester) thereof | |
| CN102910675B (en) | Preparation of VO2 nanosheet material and applications thereof | |
| CN101722017A (en) | Molybdenum-vanadium-tellurium-niobium catalytic agent for preparing acrylic acid by propane oxidation and preparation method thereof | |
| CN100563826C (en) | A kind of non-carrier vanadium-phosphorus-oxygen catalyst and method for making thereof and purposes | |
| CN1132689C (en) | Small granular size vanadium-phosphorus-oxygen catalyst and its preparation and use | |
| CN1251799C (en) | Vanadium phosphorus oxygen catalyst for preparing acrylic acid and acetic acid by oxidation of propane and preparation method thereof | |
| CN107899597A (en) | A kind of vpo catalyst and its preparation method and purposes | |
| CN111763145B (en) | Method for synthesizing acrylic acid from methyl acetate aqueous solution | |
| CN100446858C (en) | Zirconium-base loaded vanadium-phosphor oxide catalyst, and its preparing and use | |
| CN104837799A (en) | Catalytic conversion of bio-mass derivable aliphatic alcohols to valuable alkenes or oxygenates | |
| CN112973746A (en) | Preparation method of supported vanadium phosphorus oxygen catalyst, catalyst prepared by preparation method and application of catalyst | |
| CN103769182A (en) | Supported-type vanadium-phosphorus oxide, and preparation method and applications thereof | |
| CN101703941A (en) | Mo-V-Te-Nb-O composite metallic oxide catalyst as well as preparation method and application thereof | |
| CN1212893C (en) | Loaded V-P-O catalyst and its prepn and use | |
| CN1876239A (en) | Catalyst system for synthesizing acetic acid and acetic anhydride from carbonyl compound and its uses | |
| CN115090308B (en) | Metal-doped sodium super-ionic catalyst and preparation method and application thereof | |
| US9751823B2 (en) | Processes for making methacrylic acid | |
| CN1817845A (en) | Production of isooctaacid by composite catalytic method | |
| CN102850304A (en) | Furfural preparation method by using complex perovskites for one-step hydrolysis of xylan | |
| CN108503529B (en) | Method for preparing acrylic acid from propane | |
| CN111763144A (en) | Method for synthesizing acrylic acid from acetic acid | |
| CN106582744B (en) | Preparation method of catalyst for improving yield of maleic anhydride prepared by n-butane oxidation | |
| CN1701849A (en) | Method for catalytic oxidation of saturated hydrocarbons compound | |
| CN1911892A (en) | Production method of high purity niobium oxalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |