CN101058075A - Non-carrier vanadium-phosphorus-oxygen catalyst and its preparation method and use - Google Patents
Non-carrier vanadium-phosphorus-oxygen catalyst and its preparation method and use Download PDFInfo
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- CN101058075A CN101058075A CN200710022262.8A CN200710022262A CN101058075A CN 101058075 A CN101058075 A CN 101058075A CN 200710022262 A CN200710022262 A CN 200710022262A CN 101058075 A CN101058075 A CN 101058075A
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- 239000003054 catalyst Substances 0.000 title claims description 65
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 44
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 33
- 239000002202 Polyethylene glycol Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 29
- 229920001223 polyethylene glycol Polymers 0.000 claims description 29
- 239000012018 catalyst precursor Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- -1 vanadyl phosphate Chemical compound 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229940005657 pyrophosphoric acid Drugs 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000008118 PEG 6000 Substances 0.000 description 12
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 12
- 238000001994 activation Methods 0.000 description 11
- 230000003213 activating effect Effects 0.000 description 9
- 238000007605 air drying Methods 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000013467 fragmentation Methods 0.000 description 9
- 238000006062 fragmentation reaction Methods 0.000 description 9
- 238000011065 in-situ storage Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
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- 238000005516 engineering process Methods 0.000 description 5
- 208000035126 Facies Diseases 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 description 2
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- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 101150116295 CAT2 gene Proteins 0.000 description 1
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- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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Abstract
The invention relates to a non carrier vanadium phosphide oxidation accelerant, which is made of pyrophosphoric acid vanadyl with small amount of phosphoric acid sulfate and amorphous substance. The atom ratio of phosphor and vanadium is 1. 2, ratio surface area being 10-38m2/g. As positive butagas to make reaction catalyst, it works within 360-400deg.C typical temperature interval, single stroke conversion rate being 41-99%, optional rate being 60-83%, with the max recovering rate reaching 70. 2%. This invention has publicized its making formula.
Description
Technical field
The present invention relates to a kind of non-carrier vanadium-phosphorus-oxygen catalyst and on this catalyst, prepare maleic anhydride with the air catalytic oxidation normal butane.
Background technology
Maleic anhydride,, also claim maleic anhydride or cis-butenedioic anhydride, be a kind of important basic chemical industry raw material, can be used for producing unsaturated polyester resin, rich horse acid anhydride, lube oil additive, fine-chemical intermediate and specialty chemicals such as thermal resistant styrene resin, simultaneously also be production high added value fine chemicals as 1, the 4-butanediol, oxolane, the raw material of gamma-butyrolacton etc. [referring to Catal.Rev.-Sci.Eng., 27 (1985) 373 and Chem.Rev., 88 (1988) 50].
The early stage production method of cis-butenedioic anhydride is to adopt V
2O
5-MoO
3The selective oxidation preparation of catalyst by benzene.Once developing afterwards with the 1-butylene is the production process route of raw material, but original V
2O
5-MoO
3Catalyst is to the catalytic activity of 1-butene reaction system unsatisfactory [referring to Hydrocarbon Process, 11 (1980) 149].Compare with the benzene method production technology of previous employing, the butane oxidation route has obvious superiority.Therefore having stopped with benzene in developed country is the production route of raw material, and replacing butane is the production route of raw material.Present newly-built reaction unit 100% uses the butane raw material.In China, the production technology of cis-butenedioic anhydride is still relatively backward, adopts the benzene methods to produce routes also in a large number, and production scale is little, yield poorly.Along with the fast-developing of Chinese national economy and to the remarkable increase of cis-butenedioic anhydride demand, changing the production technology that falls behind at present is trend of the times.Therefore, it is very necessary to strengthen the research of this respect and technology that development has independent intellectual property right.
For catalysis butane Selective Oxidation cis-butenedioic anhydride, once attempted polytype catalyst, have only vpo catalyst the most effectively [referring to Catal.Rev.-Sci.Eng., 27 (1985) 373] up to now.Utilize vpo catalyst, the product of this reaction is except cis-butenedioic anhydride, and all the other are hydrocarbon (CO basically
x).The vpo catalyst that uses on the current industrial is non-year type, its main component be Vanadyl pyrophosphate [(VO)
2P
2O
7].The preparation vpo catalyst generally has two kinds of methods, promptly so-called water method and organic facies method.The water method is used in early stage preparation mostly, the existing organic facies methods that adopt more.The general specific area of catalyst by the preparation of organic facies method is bigger, active higher [referring to Catal.Today, 15 (1992) 407].Even use organic facies method preparation equally, because of the different of vanadium source, solvent-reducing agent, reaction temperature, dry activation condition and whether use additive etc., catalyst performance also has very big difference.This shows by improving method for preparing catalyst, can improve the performance of vpo catalyst.
Summary of the invention
The purpose of this invention is to provide the non-carrier vanadium-phosphorus oxide catalyst that the better air catalytic oxidation normal butane of a kind of catalytic activity and selectivity prepares maleic anhydride.
Technical scheme of the present invention is as follows:
A kind of non-carrier vanadium-phosphorus-oxygen catalyst, it contains a spot of vanadyl phosphate and amorphous substance phase simultaneously mainly by the phase composition of Vanadyl pyrophosphate thing, and wherein the atomic ratio of phosphorus and vanadium is 1.2, and specific area is 10-38m
2/ g.
A kind of method for preparing non-carrier vanadium-phosphorus-oxygen catalyst of the present invention, it is made up of the following step:
With the 400 ℃ of activation down in reaction mixture gas of non-carrier vanadium-phosphorus-oxygen catalyst precursor, get fresh non-carrier vanadium-phosphorus-oxygen catalyst of the present invention before using.
The above-mentioned method for preparing non-carrier vanadium-phosphorus-oxygen catalyst, in the step 1, described isobutanol and phenmethylol volume ratio can be in 0～2 scopes.
The above-mentioned method for preparing non-carrier vanadium-phosphorus-oxygen catalyst, in the step 1, described solvent adding amount and V
2O
5The ratio of input amount is 10～28ml solvent/1gV
2O
5
The purposes of non-carrier vanadium-phosphorus-oxygen catalyst of the present invention is to prepare the maleic anhydride catalyst for reaction as the air oxidation normal butane.The specific area of non-loading type vanadium-phosphor oxide catalyst of the present invention is at 10～38m
2/ g scope.Transmission electron microscope observing shows the particle size and pattern and the total amount of adding solvent and the relative quantity directly related (seeing accompanying drawing 1) of different alcohol of non-carrier vanadium-phosphorus oxidation thing.When catalyst was applied to the normal butane air oxidation and prepares cis-butenedioic anhydride, 360～400 ℃ typical reaction temperature range, its conversion per pass was 41～99%, and the cis-butenedioic anhydride selectivity is 60～83%, and the highest yield of maleic anhydride can reach 70.2%.
Description of drawings
Fig. 1 is the transmission electron microscope photo of representative catalyst.Wherein catalyst shown in Fig. 1 (a) is by 1.6 gram V
2O
5, 30ml phenmethylol and 0.80 gram PEG 6000 make (embodiment 3); Catalyst shown in Fig. 1 (b) is by 1.6 gram V
2O
5, 20ml phenmethylol+10ml isobutanol and 0.75 gram PEG 6000 make (embodiment 1); Catalyst shown in Fig. 1 (c) is by 1.6 gram V
2O
5, 10ml phenmethylol+20ml isobutanol and 0.85 gram PEG6000 make (embodiment 2); Catalyst shown in Fig. 1 (d) is by 1.6 gram V
2O
5, 12ml phenmethylol+12ml isobutanol and 0.75 the gram PEG 6000 make (embodiment 5).
Fig. 2 is the XRD figure of representative catalyst.Wherein Cat 1 catalyst shown in Fig. 2 (a) is by 1.6 gram V
2O
5, 30ml phenmethylol and 0.80 gram PEG 6000 make (embodiment 3); Cat 2 catalyst are by 1.6 gram V
2O
5, 20ml phenmethylol+10ml isobutanol and 0.75 gram PEG 6000 make (embodiment 1); Cat 3 catalyst are by 1.6 gram V
2O
5, 10ml phenmethylol+20ml isobutanol and 0.85 gram PEG 6000 make (embodiment 2); Cat 4 catalyst are by 2.0 gram V
2O
5, 25ml phenmethylol and 1.0 gram PEG 6000 make (embodiment 7).Cat 5 catalyst shown in Fig. 2 (b) are by 2.0 gram V
2O
5, 12.5ml phenmethylol+12.5ml isobutanol and 1.0 gram PEG 6000 make (embodiment 8); Cat 6 catalyst are by 2.0 gram V
2O
5, 28ml phenmethylol+28ml isobutanol and 1.45 gram PEG 6000 make (embodiment 4); Cat 7 catalyst are by 1.6 gram V
2O
5, 17.5ml phenmethylol+17.5ml isobutanol and 0.8 gram PEG 6000 make (embodiment 9); Cat 8 catalyst are by 1.6 gram V
2O
5, 12ml phenmethylol+12ml isobutanol and 0.75 gram PEG 6000 make (embodiment 5); Cat 9 catalyst are by 1.6 gram V
2O
5, 8ml phenmethylol+8ml isobutanol and 0.70 gram PEG 6000 make (embodiment 6).Among the figure:
*Be (VO)
2P
2O
7Phase, # is VOPO
42H
2The O phase.
The specific embodiment
Further specify the present invention by the following examples.
Take by weighing V
2O
51.6 restrain, place the mixed liquor of isobutanol/phenmethylol (10ml/20ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 0.75 gram, continues backflow 1 hour, presses the P/V=1.2/1.0 atomic ratio, dropping 85%H
3PO
41.5ml.Continue to reflux 6 hours.Filter, drying, the De Lanse sediment, 120 ℃ of air dryings 24 hours make catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.4～0.5MPa pressure, fragmentation, sieve is got 25～50 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating with the speed of 2 ℃/min by room temperature.Specific area is 26.3m
2/ g, VPO component are crystalline state (VO) basically
2P
2O
7(see figure 2).
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 8mm carries out catalytic performance test.In reaction temperature is 380 ℃, and air speed is 1200h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (v/v/v), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 83.5%, and the cis-butenedioic anhydride selectivity is 72.5%, and yield of maleic anhydride is 60.5%.
Embodiment 2:
Take by weighing V
2O
51.6 restrain, place the mixed liquor of isobutanol/phenmethylol (20ml/10ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 0.85 gram, continues backflow 1 hour, presses the P/V=1.2/1.0 atomic ratio, dropping 85%H
3PO
41.5ml.Continue to reflux 6 hours.Filter, drying, the De Lanse sediment, 120 ℃ of air dryings 24 hours make catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.4～0.5MPa pressure, fragmentation, sieve is got 25～50 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating with the speed of 2 ℃/min by room temperature.Specific area is 17.3m
2/ g, VPO component mainly are crystalline state (VO)
2P
2O
7, the small amount of amorphous species are also arranged simultaneously.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 8mm carries out catalytic performance test.In reaction temperature is 400 ℃, and air speed is 1200h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (v/v/v), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 85.4%, and the cis-butenedioic anhydride selectivity is 61.6%, and yield of maleic anhydride is 52.6%.
Embodiment 3:
Take by weighing V
2O
51.6 restrain, place the mixed liquor of phenmethylol (30ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 0.80 gram, continues backflow 1 hour, presses the P/V=1.2/1.0 atomic ratio, dropping 85%H
3PO
41.5ml.Continue to reflux 6 hours.Filter, drying, the De Lanse sediment, 120 ℃ of air dryings 24 hours make catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.4～0.5MPa pressure, fragmentation, sieve is got 25～50 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating with the speed of 2 ℃/min by room temperature.Specific area is 37.4m
2/ g, VPO component are well-crystallized (VO)
2P
2O
7Phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 8mm carries out catalytic performance test.In reaction temperature is 380 ℃, and air speed is 1200h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (v/v/v), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 91.0%, and the cis-butenedioic anhydride selectivity is 77.2%, and yield of maleic anhydride is 70.2%.
Embodiment 4:
Take by weighing V
2O
52.0 restrain, place the mixed liquor of isobutanol/phenmethylol (28ml/28ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 1.45 grams, continues backflow 1 hour, presses the P/V=1.2/1.0 atomic ratio, dropping 85%H
3PO
41.9ml.Continue to reflux 6 hours.Filter, drying, the De Lanse sediment, 120 ℃ of air dryings 24 hours make catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.4～0.5MPa pressure, fragmentation, sieve is got 25～50 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating with the speed of 2 ℃/min by room temperature.Specific area is 10.4m
2/ g, the VPO component mainly is amorphous phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 8mm carries out catalytic performance test.In reaction temperature is 400 ℃, and air speed is 1200h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (v/v/v), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 77.4%, and the cis-butenedioic anhydride selectivity is 62.9%, and yield of maleic anhydride is 48.7%.
Embodiment 5:
Take by weighing V
2O
51.6 restrain, place the mixed liquor of isobutanol/phenmethylol (12ml/12ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 0.75 gram, continues backflow 1 hour, presses the P/V=1.2/1.0 atomic ratio, dropping 85%H
3PO
41.5ml.Continue to reflux 6 hours.Filter, drying, the De Lanse sediment, 120 ℃ of air dryings 24 hours make catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.4～0.5MPa pressure, fragmentation, sieve is got 25～50 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating with the speed of 2 ℃/min by room temperature.Specific area is 22.9m
2/ g, the VPO component mainly is (VO)
2P
2O
7Crystalline phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 8mm carries out catalytic performance test.In reaction temperature is 360 ℃, and air speed is 1200h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (v/v/v), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 70.0%, and the cis-butenedioic anhydride selectivity is 80.0%, and yield of maleic anhydride is 56.0%.
Embodiment 6:
Take by weighing V
2O
51.6 restrain, place the mixed liquor of isobutanol/phenmethylol (8ml/8ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 0.70 gram, continues backflow 1 hour, presses the P/V=1.2/1.0 atomic ratio, dropping 85%H
3PO
41.5ml.Continue to reflux 6 hours.Filter, drying, the De Lanse sediment, 120 ℃ of air dryings 24 hours make catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.4～0.5MPa pressure, fragmentation, sieve is got 25～50 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating with the speed of 2 ℃/min by room temperature.Specific area is 18.0m
2/ g, the VPO component mainly is amorphous phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 8mm carries out catalytic performance test.In reaction temperature is 380 ℃, and air speed is 1200h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (v/v/v), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 66.8%, and the cis-butenedioic anhydride selectivity is 77.0%, and yield of maleic anhydride is 51.4%.
Embodiment 7:
Take by weighing V
2O
52.0 restrain, place the mixed liquor of isobutanol/phenmethylol (0ml/25ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 1.00 grams, continues backflow 1 hour, presses the P/V=1.2/1.0 atomic ratio, dropping 85%H
3PO
41.9ml.Continue to reflux 6 hours.Filter, drying, the De Lanse sediment, 120 ℃ of air dryings 24 hours make catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.4～0.5MPa pressure, fragmentation, sieve is got 25～50 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating with the speed of 2 ℃/min by room temperature.Specific area is 25.8m
2/ g, VPO component are well-crystallized (VO)
2P
2O
7Phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 8mm carries out catalytic performance test.In reaction temperature is 400 ℃, and air speed is 1200h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (v/v/v), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 92.3%, and the cis-butenedioic anhydride selectivity is 72.7%, and yield of maleic anhydride is 67.9%.
Embodiment 8:
Take by weighing V
2O
52.0 restrain, place the mixed liquor of isobutanol/phenmethylol (12.5/12.5ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 1.00 grams, continues backflow 1 hour, presses the P/V=1.2/1.0 atomic ratio, dropping 85%H
3PO
41.9ml.Continue to reflux 6 hours.Filter, drying, the De Lanse sediment, 120 ℃ of air dryings 24 hours make catalyst precursor powder.The catalyst precursor powder that makes is pressed into sheet under 0.4～0.5MPa pressure, fragmentation, sieve is got 25～50 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating with the speed of 2 ℃/min by room temperature.Specific area is 18.8m
2/ g, VPO component are (VO)
2P
2O
7Crystalline phase and amorphous substance partly are mutually.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 8mm carries out catalytic performance test.In reaction temperature is 400 ℃, and air speed is 1200h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (v/v/v), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 89.7%, and the cis-butenedioic anhydride selectivity is 68.8%, and yield of maleic anhydride is 61.5%.
Embodiment 9:
Take by weighing V
2O
51.6 restrain, place the mixed liquor of isobutanol/phenmethylol (17.5/17.5ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 0.80 gram, continues backflow 1 hour, presses the P/V=1.2/1.0 atomic ratio, dropping 85%H
3PO
41.5ml.Continue to reflux 6 hours.Filter, drying, De Lanse sediment, 120 ℃ of air dryings 24 hours.The catalyst precursor powder that makes is pressed into sheet under 0.4～0.5MPa pressure, fragmentation, sieve is got 25～50 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating with the speed of 2 ℃/min by room temperature.Specific area is 18.8m
2/ g, VPO component are (VO)
2P
2O
7Crystalline phase and amorphous substance partly are mutually.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 8mm carries out catalytic performance test.In reaction temperature is 380 ℃, and air speed is 1200h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (v/v/v), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 66.0%, and the cis-butenedioic anhydride selectivity is 66.5%, and yield of maleic anhydride is 43.9%.
Claims (5)
1. non-carrier vanadium-phosphorus-oxygen catalyst, it is characterized in that: it contains a spot of vanadyl phosphate and amorphous substance phase simultaneously mainly by the phase composition of Vanadyl pyrophosphate thing, and wherein the atomic ratio of phosphorus and vanadium is 1.2, and specific area is 10-38m
2/ g.
2. method for preparing the described non-carrier vanadium-phosphorus-oxygen catalyst of claim 1 is characterized in that it is made up of the following step:
Step 1. is mixed vanadic anhydride with phenmethylol or isobutanol-phenmethylol mixed alcohol, added hot reflux 6 hours,
Step 2. adds polyethylene glycol, continues to reflux 1 hour, and the polyethylene glycol of described adding is that molecular weight is 6000 polyethylene glycol, and the amount that adds polyethylene glycol is V
2O
5With the mass ratio of polyethylene glycol be 1.38: 1～2.29: 1,
Step 3. adds phosphoric acid, and the addition of phosphoric acid is that to make the atomic ratio of phosphorus and vanadium be 1.2: 1.0, and the phosphoric acid of adding is that mass percent is 85% phosphoric acid, continues to reflux 6 hours, and there is blue look to precipitate in the course of reaction gradually and separates out,
Step 4. is cooled to room temperature with reactant mixture, leaves standstill 3～5 hours, filters, and leaches thing with isobutanol and acetone washing, leaches thing and be warming up to 120 ℃ of dryings in air atmosphere, promptly gets non-carrier vanadium-phosphorus-oxygen catalyst precursor of the present invention,
Before using, step 5., gets fresh non-carrier vanadium-phosphorus-oxygen catalyst with the 400 ℃ of activation down in reaction mixture gas of non-carrier vanadium-phosphorus-oxygen catalyst precursor.
3. the method for preparing non-carrier vanadium-phosphorus-oxygen catalyst according to claim 2 is characterized in that: in the described step 1, described isobutanol and phenmethylol volume ratio are 0～2.
4. the method for preparing non-carrier vanadium-phosphorus-oxygen catalyst according to claim 2 is characterized in that: in the described step 1, and described solvent adding amount and V
2O
5The ratio of input amount is 10～28ml solvent/1g V
2O
5
5. the purposes of the described non-carrier vanadium-phosphorus-oxygen catalyst of claim 1 is characterized in that: prepare the maleic anhydride catalyst for reaction as the air oxidation normal butane.
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| CNB2007100222628A CN100563826C (en) | 2007-05-11 | 2007-05-11 | A kind of non-carrier vanadium-phosphorus-oxygen catalyst and method for making thereof and purposes |
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| CNB2007100222628A CN100563826C (en) | 2007-05-11 | 2007-05-11 | A kind of non-carrier vanadium-phosphorus-oxygen catalyst and method for making thereof and purposes |
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| 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 |
| CN103537310A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Catalyst and method for preparing maleic anhydride by normal butane oxidization |
| CN103801349A (en) * | 2014-03-19 | 2014-05-21 | 南京大学 | Vanadium phosphorus oxide (VPO) catalyst and application thereof in preparation of acraldehyde from glycerol in dewatering manner |
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| CN103949277B (en) * | 2014-05-21 | 2016-05-25 | 厦门大学 | The support type Vanadyl pyrophosphate Catalysts and its preparation method of selective oxidation of n-butane |
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