CN100446858C - Zirconium-base loaded vanadium-phosphor oxide catalyst, and its preparing and use - Google Patents
Zirconium-base loaded vanadium-phosphor oxide catalyst, and its preparing and use Download PDFInfo
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- CN100446858C CN100446858C CNB2006100967369A CN200610096736A CN100446858C CN 100446858 C CN100446858 C CN 100446858C CN B2006100967369 A CNB2006100967369 A CN B2006100967369A CN 200610096736 A CN200610096736 A CN 200610096736A CN 100446858 C CN100446858 C CN 100446858C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 40
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 36
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 30
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012876 carrier material Substances 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 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
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 26
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 26
- 229920001223 polyethylene glycol Polymers 0.000 claims description 26
- 238000010992 reflux Methods 0.000 claims description 24
- -1 Vanadyl pyrophosphate Chemical compound 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 235000011180 diphosphates Nutrition 0.000 claims description 13
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 13
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000005303 weighing Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 230000007935 neutral effect Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000001994 activation Methods 0.000 description 10
- 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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- 239000013049 sediment Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- 235000013844 butane Nutrition 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000001273 butane Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000003993 interaction Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960000800 cetrimonium bromide Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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Abstract
The present invention relates to a catalyst made up by using zirconium base carrier material or zirconium base carrier material modified by phosphoric acid and vanadium phosphorus oxide loaded on said carrier material. The described zirconium base carrier material is zirconium oxide, the loaded quantity of vanadium phosphorus oxide is 25-47 wt% of total mass of said catalyst, in which the atomic ratio of vanadium and phosphorus is 1.2, its specific surface area is about 21-29 sq.m/g. When it is used as catalyst for normal-butane air oxidation reaction to prepare cis-butenedioic anhydride, in the typical reaction temperature zone of 380-420deg.C its per pass conversion rate is 38-89%, the cis-butenedioic anhydride selectivity is 29-69% and maximum cis-butenedioic anhydride yield is 61.2%. Said invention also discloses the preparation method of said catalyst.
Description
Technical field
The present invention relates to the load-type vanadium phosphorus oxide catalyst and on such catalyst, prepare maleic anhydride with the air catalytic oxidation normal butane.
Background technology
Maleic anhydride, be called for short cis-butenedioic anhydride, also claim maleic anhydride, it is a kind of important chemical 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 also are that production high added value fine chemicals is as 1 simultaneously, the 4-butanediol, oxolane, the raw material of gamma-butyrolacton etc., its range of application is still constantly enlarging [referring to Catal.Rev.-Sci.Eng. at present, 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].The someone found vanadium composite phosphorus oxide (VPO) catalysis normal butane selective oxidation generation cis-butenedioic anhydride [US Patent 3293268 (1966)] effectively afterwards.But because therefore the resource of butane did not seldom have competitiveness in industrial this course of reaction at that time.Subsequently because a large amount of exploitations of natural gas make butane have abundant source and price also day by day cheap.In addition, from point of view of environment protection, compare with the benzene method production technology of previous employing, the butane oxidation route also has obvious superiority.Therefore developed country such as America and Europe progressively to stop with benzene be the production route of raw material, replacing butane is the production route of raw material.100% use the butane raw material at the newly-built reaction unit of western countries.In China, the production technology of cis-butenedioic anhydride is still relatively backward, also adopt the benzene method to produce route basically, and scale is less than normal, output is lower.Along with the fast-developing of Chinese national economy and to the obvious increase of cis-butenedioic anhydride demand, the production technology that changes original backwardness is imperative.Therefore, strengthen the science and technology research of this respect and develop technology and be very important with independent intellectual property right.
For the reaction of catalysis butane Selective Oxidation cis-butenedioic anhydride, people attempted the catalyst of many types, but had only vpo catalyst up to now to this reaction the most effectively [referring to Catal.Rev.-Sci.Eng., 27 (1985) 373].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].With respect to non-supported catalyst, loaded catalyst has some characteristics: the surface area/volume ratio that 1. can improve active phase (active constituent); 2. can improve the mechanical strength of catalyst usually; 3. can improve the hot mass transfer of catalyst.For this reason, existing many researchers attempt preparing the catalyst of support type, and used carrier comprises conventional SiO
2, TiO
2, Al
2O
3, SiC, Al-MCM-41, SBA-15 etc., however the performance of its unit mass catalyst of prepared loaded catalyst all be lower than non-supported catalyst [referring to J.Phys.Chem.B, 101 (1997) 6895; Appl.Catal.A, 135 (1996) 231; Appl.Catal.A, 135 (1996) 209; React.Kinet.Catal.Lett., 32 (1986) 209; Catal.Lett., 28 (1994) 1; Catal.Lett., 76 (2001) 3; J.Catal., 238 (2006) 232].Result of study will produce interaction after showing the use carrier between carrier and supported V PO, and this interaction may be prevented the desirable specific VPO thing phase of formation, thereby causes the reduction of catalytic performance.This character that shows the selection of carrier and carrier itself is very important to developing this class loaded catalyst.It is found that, when VPO being loaded to reducible carrier (as TiO
2) when going up [referring to Appl.Catal.A, 135 (1996) 209; Appl.Catal.A, 135 (1996) 231], it and carrier interactions are stronger, and also easier being reduced itself, so its catalytic activity is significantly improved but selectivity significantly descends; And when VPO being loaded on the carrier of relative natural instincts (as SiO
2), a little less than the interaction between it and the carrier, this moment, selection of catalysts was improved but active decline.On the other hand, result of study shows also that when with water immersion process for preparing support type vpo catalyst the more V of containing is arranged in the sample
5+Phosphate, mainly be α-VOPO
4And γ-VOPO
4Butanes conversion and cis-butenedioic anhydride selectivity are all lower on this class supported catalyst, such as at conventional SiO
2Its butanes conversion of supported V PO catalyst that goes up with the preparation of water dipping method is about 50%, and the cis-butenedioic anhydride selectivity then is lower than 20%[referring to J.Phys.Chem.B, and 101 (1997) 6895].This shows that the improvement of method for preparing catalyst also can improve the performance of support type vpo catalyst.
Summary of the invention
The purpose of this invention is to provide the better support type vpo catalyst of a kind of performance, be characterized in: 1. ZrO
2Be a class multifunctional material,, be widely used in such as hydrocarbon-selective reducing nitrogen oxides (NO as catalyst carrier or carrier component
x) [referring to J.Catal.221 (2004) 594], three-way catalyst is [referring to Catal.Lett.72 (2001) 39; J.Catal.221 (2004) 148], methyl alcohol synthesizes and decomposes [referring to J.Catal.178 (1998) 153; J.Catal.193 (2000) 207; Appl.Catal.A:Gen.171 (1998) 123], co hydrogenation [referring to Appl.Catal.A:Gen.213 (2001) 225], partial oxidation of methane [referring to Catal.Lett.51 (1998) 163], methanol steam are reformed [referring to Catal.43 (1988) 141; Catal.Today 51 (1999) 521] and prepare the sulfated zirconia solid strong acid [referring to J.Catal.151 (1995) 364; J.Catal.196 (2000) 104].The zirconium base carrier material that the present invention adopts the Zirconia carrier material first or modifies through phosphoric acid; 2. adopt that co-deposition method prepares supported catalyst in organic facies, can avoid generating the more V that contains
5+Phosphate; 3. in the preparation medium, add larger molecular organics, make the dispersion of loaded vanadium-phosphor oxide more even; 4. catalyst not only has high catalytic activity, still can keep simultaneously comparatively ideal cis-butenedioic anhydride selectivity, therefore is the highest class support type vpo catalyst of yield of maleic anhydride so far.
Technical scheme of the present invention is as follows:
A kind of Zirconium-base loaded vanadium-phosphor oxide catalyst, the zirconium base carrier material load vanadium phosphorus oxide that it is modified by zirconium base carrier material or phosphoric acid constitutes, zirconium base carrier material is a zirconia, the load capacity of vanadium phosphorus oxide is preferably 25～46wt% of catalyst gross mass in Vanadyl pyrophosphate, wherein the atomic ratio of phosphorus and vanadium is 1.2, and specific area is 21-29m
2/ g, the vanadium phosphorus oxide of load are Vanadyl pyrophosphate crystalline phase or amorphous substance phase, and contain a certain amount of vanadyl phosphate species.
A kind of method for preparing loaded vanadium-phosphor oxide catalyst of the present invention, it is made up of the following step:
A. the preparation of zirconium base carrier:
A.1 with ZrOCl
28H
2O and CTAB (cetrimonium bromide) are that 4～5: 1 ratio is soluble in water in mass ratio, stirring obtains a settled solution, and dripping concentration lentamente in this solution after 70 ℃ 2h is stirred in continuation down is the NaOH solution of 2mol/L, regulates pH to 12-14, obtain a leucosol gel
A.2 this mixture being transferred in the autoclave and behind 100 ℃ of following constant temperature 48h and naturally cooled to room temperature, with the washing of gained white solid, filtration, is neutral until filtrate,
A.3 with the gained white solid earlier 100 ℃ of oven dry down, then in air atmosphere by room temperature with the speed of 1 ℃/min rise to 550 ℃ and under this temperature constant temperature 8h.Obtain zirconium base carrier material thus, be designated as ZrO
2
B. the preparation of the zirconium base carrier material of phosphoric acid modification:
B.1 steps A .2 is obtained through the white solid of hydrothermal treatment consists 100 ℃ of oven dry, use H then
3PO
4(0.5～1.5mol/L), the every gram of solid-like adds H to solution-treated
3PO
4Solution 20ml stirs 12h at 70 ℃ of following constant temperature, and the sample that will handle repeatedly washs then, is neutral until filtrate.With step A.3 roasting condition obtains the zirconium base carrier material that phosphoric acid is modified thus, is designated as H
3PO
4-p-ZrO
2
B.2 the zirconium base carrier material ZrO that will make by steps A .3
2Use H
3PO
4(0.5～1.5mol/L), the every gram of solid-like adds H to solution-treated
3PO
4Solution 20ml.Stir 12h at 70 ℃ of following constant temperature, the sample that will handle repeatedly washs then, is neutral until filtrate.Dry resulting sample, roasting condition with step A.3.Obtain the zirconium base carrier material that phosphoric acid is modified thus, be designated as H
3PO
4-ZrO
2
C. the preparation of Zirconium-base loaded vanadium-phosphor oxide compound catalyst
C.1 vanadic anhydride is mixed with isobutanol-phenmethylol mixed solvent, added hot reflux 6 hours,
C.2 add a certain amount of polyethylene glycol, add an amount of zirconium base carrier (ZrO again
2) or the zirconium base carrier (H that modifies of phosphoric acid
3PO
4-p-ZrO
2Or H
3PO
4-ZrO
2), continue to reflux 0.5 hour,
C.3 add phosphoric acid, 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 can be the phosphoric acid of 85% (m/m), continues to reflux 7 hours, has blue look precipitation to separate out in the course of reaction gradually,
C.4 reactant mixture is cooled to room temperature, left standstill 2～5 hours, filter, with isobutanol and acetone washing and filtering thing several, filtrate is warming up to 120 ℃ of dryings in air atmosphere, promptly get Zirconium-base loaded vanadium-phosphor oxide catalyst precursor of the present invention,
C.5 400 ℃ of activation down in reaction mixture gas get fresh Zirconium-base loaded vanadium-phosphor oxide catalyst of the present invention before using.
The above-mentioned method for preparing Zirconium-base loaded vanadium-phosphor oxide catalyst, step C.1 in, described isobutanol-phenmethylol mixed solvent is mixed by the phenmethylol of the isobutanol of 1 part of volume and 1 part of volume and forms.
The above-mentioned method for preparing Zirconium-base loaded vanadium-phosphor oxide catalyst, step C.2 in, the polyethylene glycol of described adding is that molecular weight is 2000～6000 polyethylene glycol, adding the amount of polyethylene glycol and the mass ratio of vanadic anhydride is 45.8: 100～77.5: 100.
The purposes of load-type vanadium phosphor oxide catalyst of the present invention is to prepare the cis-butenedioic anhydride catalyst for reaction as the air oxidation normal butane.The specific area of load-type vanadium phosphor oxide catalyst of the present invention is at 23～36m
2/ g scope.Transmission electron microscope observing finds that the vanadium phosphorus oxide of load disperses relatively evenly (seeing accompanying drawing 1) on carrier material.Method for preparing catalyst is easier.When being applied to the normal butane air oxidation and preparing cis-butenedioic anhydride, 380～420 ℃ typical reaction temperature range, its conversion per pass is 38～89%, and the cis-butenedioic anhydride selectivity is 29～69%, and the highest yield of maleic anhydride is 61.2%.
Description of drawings
Fig. 1 is the transmission electron microscope photo of catalyst: (a) overall picture: (b): individual particle.
Fig. 2 is the XRD figure of representative catalyst.
The specific embodiment
Further specify the present invention by the following examples.
Embodiment 1
With 5.00g ZrOCl
28H
2O and 1.00g CTAB are soluble in water, stir to obtain a settled solution, drip the NaOH solution of 2mol/L lentamente in this solution after 70 ℃ 2h is stirred in continuation down, and regulate PH 〉=12.00, obtain a leucosol gel.This mixture transferred in the autoclave and behind 100 ℃ of following constant temperature 48h naturally cool to room temperature.Solids is filtered, washs, and is neutral to pH value of filtrate.Then resulting white solid is dried down in 100 ℃.With this white solid in air with the speed of 1 ℃/min by room temperature rise to 550 ℃ and under this temperature constant temperature calcining 8h.Obtain zirconium base carrier thus without the phosphoric acid modification.
Take by weighing V
2O
52.4 restrain, place the mixed liquor of isobutanol/phenmethylol (30ml/30ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 2000 polyethylene glycol (PEG2000) 1.1 grams, and adding 6.0 restrains the zirconium base carrier ZrO of above-mentioned preparation
2, continue to reflux 0.5 hour, press the P/V=1.2/1.0 atomic ratio, drip 85%H
3PO
42.2ml.Continue to reflux 7 hours.Filtration, drying, De Lanse sediment, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 40～60 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 25.6m
2/ g, supported V PO component is amorphous state substantially.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm 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), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 38.4%, and the cis-butenedioic anhydride selectivity is 36.1%, and yield of maleic anhydride is 13.8%.
Embodiment 2:
With 4.00g ZrOCl
28H
2O and 1.00g CTAB are soluble in water, stir to obtain a settled solution, drip the NaOH solution of 2mol/L lentamente in this solution after 70 ℃ 2h is stirred in continuation down, and regulate PH 〉=12.00, obtain a leucosol gel.This mixture transferred in the autoclave and behind 100 ℃ of following constant temperature 48h naturally cool to room temperature.Solids is filtered, washs, and is neutral to pH value of filtrate.Then resulting white solid is dried down in 100 ℃, place the H of 1mol/L
3PO
4In the solution, the every gram of solid-like adds H
3PO
4Solution 20ml stirs 12h at 70 ℃ of following constant temperature, and the sample filtering that will handle, washing then is neutral to filtrate, 100 ℃ of oven dry.In air with the speed of 1 ℃/min by room temperature rise to 550 ℃ and under this temperature constant temperature calcining 8h.Obtain zirconium base carrier thus through the phosphoric acid modification.
Take by weighing V
2O
50.8 gram places the mixed liquor of isobutanol/phenmethylol (10ml/10ml), 140 ℃ refluxed 6 hours after, add molecular weight and be 6000 polyethylene glycol (PEG6000) 0.37 gram, add the zirconium base carrier (H that 2.0 grams are modified through phosphoric acid by the precursor of above-mentioned preparation
3PO
4-p-ZrO
2), continue to reflux 0.5 hour, press the P/V=1.2/1.0 atomic ratio, drip 85%H
3PO
40.72ml.Continue to reflux 7 hours.Filtration, drying, De Lanse sediment, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 40～60 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating by room temperature with the speed of 2 ℃/min in 1.5/17.2/81.3).Specific area is 24.2m
2/ g, supported V PO component is the Vanadyl pyrophosphate crystalline phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm 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), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 89.1%, and the cis-butenedioic anhydride selectivity is 68.8%, and yield of maleic anhydride is 61.2%.
Embodiment 3:
With 4.00g ZrOCl
28H
2O and 1.00g CTAB are soluble in water, stir to obtain a settled solution, drip the NaOH solution of 2mol/L lentamente in this solution after 70 ℃ 2h is stirred in continuation down, and regulate PH 〉=12.00, obtain a leucosol gel.This mixture transferred in the autoclave and behind 100 ℃ of following constant temperature 48h naturally cool to room temperature.Solids is filtered, washs, and is neutral to pH value of filtrate.Then with resulting white solid in 100 ℃ of down oven dry, in air with the speed of 1 ℃/min by room temperature rise to 550 ℃ and under this temperature constant temperature calcining 8h.Solid after the experience roasting is placed the H of 1mol/L
3PO
4In the solution, every gram solid-like adds H
3PO
4Solution 20ml stirs 12h at 70 ℃ of following constant temperature, then with sample filtering, washing, is neutral to filtrate, and 100 ℃ of oven dry, roasting under above-mentioned the same terms again obtains the zirconium base carrier (H that modifies through phosphoric acid
3PO
4-ZrO
2).
Take by weighing V
2O
50.8 restrain, place the mixed liquor of isobutanol/phenmethylol (10ml/10ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 0.37 gram, and adding 2.0 restrains the phosphoric acid modification zirconium base carrier H of above-mentioned preparation
3PO
4-ZrO
2, continue to reflux 0.5 hour, press the P/V=1.2/1.0 atomic ratio, drip 85%H
3PO
40.72ml.Continue to reflux 7 hours.Filtration, drying, De Lanse sediment, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 40～60 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating by room temperature with the speed of 2 ℃/min in 1.5/17.2/81.3).Specific area is 22.8m
2/ g, supported V PO component are the low Vanadyl pyrophosphate crystalline phase of crystallinity.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm carries out catalytic performance test.In reaction temperature is 420 ℃, 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), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 71.9%, and the cis-butenedioic anhydride selectivity is 54.2%, and yield of maleic anhydride is 39.0%.
Embodiment 4:
Take by weighing V
2O
50.8 restrain, place the mixed liquor of isobutanol/phenmethylol (10ml/10ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 2000 polyethylene glycol (PEG2000) 0.62 gram, adds 2.0 and restrains the phosphoric acid modification zirconium base carrier H that prepared by embodiment 2
3PO
4-p-ZrO
2, continue to reflux 0.5 hour, press the P/V=1.2/1.0 atomic ratio, drip 85%H
3PO
40.72ml.Continue to reflux 7 hours.Filtration, drying, De Lanse sediment, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 40～60 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating by room temperature with the speed of 2 ℃/min in 1.5/17.2/81.3).Specific area is 23.5m
2/ g, supported V PO component is the Vanadyl pyrophosphate crystalline phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm carries out catalytic performance test.In reaction temperature is 400 ℃, and air speed is 1800h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (V/V), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 80.5%, and the cis-butenedioic anhydride selectivity is 71.2%, and yield of maleic anhydride is 57.3%.
Embodiment 5:
Take by weighing 0.4 gram V
2O
5, place the mixed liquor of isobutanol/phenmethylol (10ml/10ml), 140 ℃ refluxed 6 hours after, add molecular weight and be 6000 polyethylene glycol (PEG6000) 0.37 gram, add 2.0 grams and modify zirconium base carrier H by the phosphoric acid of embodiment 2 preparations
3PO
4-p-ZrO
2, continue to reflux 0.5 hour, press the P/V=1.2/1.0 atomic ratio, drip 85%H
3PO
40.72ml.Continue to reflux 7 hours.Filtration, drying, De Lanse sediment, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 40～60 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating by room temperature with the speed of 2 ℃/min in 1.5/17.2/81.3).Specific area is 28.6m
2/ g, supported V PO component is the Vanadyl pyrophosphate crystalline phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm 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), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 58.7%, and the cis-butenedioic anhydride selectivity is 58.5%, and yield of maleic anhydride is 34.3%.
Embodiment 6:
Take by weighing V
2O
52.0 restrain, place the mixed liquor of isobutanol/phenmethylol (20ml/20ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 1.1 grams, adds 4.0 and restrains the phosphoric acid modification zirconium base carrier H that prepared by embodiment 2
3PO
4-p-ZrO
2, continue to reflux 0.5 hour, press the P/V=1.2/1.0 atomic ratio, drip 85%H
3PO
40.72ml.Continue to reflux 7 hours.Filtration, drying, De Lanse sediment, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 40～60 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating by room temperature with the speed of 2 ℃/min in 1.5/17.2/81.3).Specific area is 20.5m
2/ g, supported V PO component is the Vanadyl pyrophosphate crystalline phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm 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), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 78.3%, and the cis-butenedioic anhydride selectivity is 58.7%, and yield of maleic anhydride is 46.0%.
Embodiment 7:
Take by weighing V
2O
50.8 restrain, place the mixed liquor of isobutanol/phenmethylol (10ml/10ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 0.37 gram, adds 2.0 and restrains the phosphoric acid modification zirconium base carrier H that prepared by embodiment 2
3PO
4-p-ZrO
2, continue to reflux 0.5 hour, press the P/V=1.2/1.0 atomic ratio, drip 85%H
3PO
40.72ml.Continue to reflux 7 hours.Filtration, drying, De Lanse sediment, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 40～60 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating by room temperature with the speed of 2 ℃/min in 1.5/17.2/81.3).Specific area is 24.2m
2/ g, supported V PO component is the Vanadyl pyrophosphate crystalline phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm carries out catalytic performance test.In reaction temperature is 400 ℃, and air speed is 3000h
-1, unstripped gas consists of C
4H
10/ O
2/ N
2React under the condition of=1.5/17.2/81.3 (V/V), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 60.2%, and the cis-butenedioic anhydride selectivity is 70.7%, and yield of maleic anhydride is 42.5%.
Embodiment 8:
With 4.00g ZrOCl
28H
2O and 1.00g CTAB are soluble in water, stir to obtain a settled solution, drip the NaOH solution of 2mol/L lentamente in this solution after 70 ℃ 2h is stirred in continuation down, and regulate PH 〉=12.00, obtain a leucosol gel.This mixture transferred in the autoclave and behind 100 ℃ of following constant temperature 48h naturally cool to room temperature.Solids is filtered, washs, and is neutral to pH value of filtrate.Then resulting white solid is dried down in 100 ℃, place the H of 1.5mol/L
3PO
4In the solution, the every gram of solid-like adds H
3PO
4Solution 20ml stirs 12h at 70 ℃ of following constant temperature, and the sample filtering that will handle, washing then is neutral to filtrate, 100 ℃ of oven dry.In air with the speed of 1 ℃/min by room temperature rise to 550 ℃ and under this temperature constant temperature calcining 8h.Obtain the zirconium base carrier that phosphoric acid is modified thus.
Take by weighing V
2O
50.8 restrain, place the mixed liquor of isobutanol/phenmethylol (10ml/10ml), 140 ℃ of backflows are after 6 hours, and the adding molecular weight is 6000 polyethylene glycol (PEG6000) 0.37 gram, adds the 2.0 zirconium base carrier H that restrain by the phosphoric acid modification of above-mentioned preparation
3PO
4-p-ZrO
2, continue to reflux 0.5 hour, press the P/V=1.2/1.0 atomic ratio, drip 85%H
3PO
40.72ml.Continue to reflux 7 hours.Filtration, drying, De Lanse sediment, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 40～60 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating by room temperature with the speed of 2 ℃/min in 1.5/17.2/81.3).Supported V PO component is the Vanadyl pyrophosphate crystalline phase.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm 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), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 67.5%, and the cis-butenedioic anhydride selectivity is 34.0%, and yield of maleic anhydride is 22.9%.
Embodiment 9:
With 4.00g ZrOCl
28H
2O and 1.00g CTAB are soluble in water, stir to obtain a settled solution, drip the NaOH solution of 2mol/L lentamente in this solution after 70 ℃ 2h is stirred in continuation down, and regulate PH 〉=12.00, obtain a leucosol gel.This mixture transferred in the autoclave and behind 100 ℃ of following constant temperature 48h naturally cool to room temperature.Solids is filtered, washs, and is neutral to pH value of filtrate.Then resulting white solid is dried down in 100 ℃, place the H of 0.5mol/L
3PO
4In the solution, the every gram of solid-like adds H
3PO
4Solution 20ml stirs 12h at 70 ℃ of following constant temperature, and the sample filtering that will handle, washing then is neutral to filtrate, 100 ℃ of oven dry.In air with the speed of 1 ℃/min by room temperature rise to 550 ℃ and under this temperature constant temperature calcining 8h.Obtain the zirconium base carrier that phosphoric acid is modified thus.
Take by weighing V
2O
51.6 gram places the mixed liquor of isobutanol/phenmethylol (20ml/20ml), 140 ℃ refluxed 6 hours after, add molecular weight and be 6000 polyethylene glycol (PEG6000) 1.1 grams, add 4.0 grams and modify zirconium base carrier H through phosphoric acid by the precursor of above-mentioned preparation
3PO
4-p-ZrO
2, continue to reflux 0.5 hour, press the P/V=1.2/1.0 atomic ratio, drip 85%H
3PO
40.72ml.Continue to reflux 7 hours.Filtration, drying, De Lanse sediment, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 40～60 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=rise to 400 ℃ of in-situ activations 15 hours, the fresh catalyst that obtains activating by room temperature with the speed of 2 ℃/min in 1.5/17.2/81.3).Supported V PO component is the lower Vanadyl pyrophosphate crystalline phase of crystallinity.
Take by weighing activated fresh catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm 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), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 78.3%, and the cis-butenedioic anhydride selectivity is 58.7%, and yield of maleic anhydride is 46.0%.
Claims (8)
1. Zirconium-base loaded vanadium-phosphor oxide catalyst, it is characterized in that: it is made of zirconium base carrier material load vanadium phosphorus oxide, zirconium base carrier material is a zirconia, the load capacity of vanadium phosphorus oxide is counted 25～46wt% of catalyst gross mass with Vanadyl pyrophosphate, wherein the atomic ratio that feeds intake of phosphorus and vanadium is 1.2, and specific area is 21-29m
2/ g, the vanadium phosphorus oxide of load are Vanadyl pyrophosphate crystalline phase or amorphous substance phase, and contain the vanadyl phosphate species.
2. Zirconium-base loaded vanadium-phosphor oxide catalyst according to claim 1 is characterized in that: described zirconium base carrier material is the zirconium base carrier material that phosphoric acid is modified.
3. method for preparing the described Zirconium-base loaded vanadium-phosphor oxide catalyst of claim 1 is characterized in that it is made up of the following step:
Step 1. is mixed vanadic anhydride with isobutanol-phenmethylol mixed solvent, added hot reflux 6 hours,
Step 2. adds polyethylene glycol, adds the zirconium base carrier again, continue to reflux 0.5 hour,
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, continues to reflux 7 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 2～5 hours, filters, and leaches thing with isobutanol and acetone washing, and the thing that leaches after the washing is warming up to 120 ℃ of dryings in air atmosphere, promptly get the Zirconium-base loaded vanadium-phosphor oxide catalyst precursor,
Before using, step 5., gets fresh Zirconium-base loaded vanadium-phosphor oxide catalyst with the 400 ℃ of activation down in reaction mixture gas of Zirconium-base loaded vanadium-phosphor oxide catalyst precursor.
4. the method for preparing Zirconium-base loaded vanadium-phosphor oxide catalyst according to claim 3 is characterized in that: in the step 1, described isobutanol-phenmethylol mixed solvent is made up of the isobutanol of 1 part of volume and the phenmethylol mixing of 1 part of volume.
5. the method for preparing Zirconium-base loaded vanadium-phosphor oxide catalyst according to claim 3, it is characterized in that: in the step 2, the polyethylene glycol of described adding is that molecular weight is 2000～6000 polyethylene glycol, and adding the quality of polyethylene glycol and the mass ratio of vanadic anhydride is 45.8: 100～77.5: 100.
6. the method for preparing Zirconium-base loaded vanadium-phosphor oxide catalyst according to claim 3 is characterized in that: in the step 2, described zirconium base carrier is the zirconium base carrier that phosphoric acid is modified.
7. the method for preparing Zirconium-base loaded vanadium-phosphor oxide catalyst according to claim 3 is characterized in that: in the step 3, the phosphoric acid of described adding is that mass percentage concentration is 85% phosphoric acid.
8. the purposes of Zirconium-base loaded vanadium-phosphor oxide catalyst according to claim 1 is to prepare the cis-butenedioic anhydride catalyst for reaction as the air oxidation normal butane.
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| 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 |
| CN104557817B (en) * | 2013-10-28 | 2017-05-24 | 中国石油化工股份有限公司 | Method for preparing maleic anhydride through n-butane |
| CN104607221B (en) * | 2013-11-05 | 2017-02-08 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide and preparation method thereof |
| CN104607219B (en) * | 2013-11-05 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of vanadium-phosphor oxide catalyst of butane oxidation cis-butenedioic anhydride and preparation method thereof |
| 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 |
| CN106140125B (en) * | 2015-04-24 | 2019-03-26 | 中国石油化工股份有限公司 | A kind of support type catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof |
| CN106492862B (en) * | 2015-09-08 | 2019-04-16 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof being used to prepare cis-butenedioic anhydride |
| CN109046413B (en) * | 2018-08-23 | 2022-05-03 | 常州新日催化剂股份有限公司 | Catalyst for preparing maleic anhydride by n-butane oxidation and preparation method thereof |
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| US3888886A (en) * | 1972-06-08 | 1975-06-10 | Mobil Oil Corp | Oxidation of alkanes to maleic anhydride using promoted vanadium-phosphorus catalyst |
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| CN1282631A (en) * | 2000-05-17 | 2001-02-07 | 中国石油化工集团公司 | V-P-O catalyst for preparing cis-anhydride by selective oxidation of n-butane and its preparing process |
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2006
- 2006-10-13 CN CNB2006100967369A patent/CN100446858C/en not_active Expired - Fee Related
Patent Citations (5)
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|---|---|---|---|---|
| US3888886A (en) * | 1972-06-08 | 1975-06-10 | Mobil Oil Corp | Oxidation of alkanes to maleic anhydride using promoted vanadium-phosphorus catalyst |
| US3932305A (en) * | 1974-04-17 | 1976-01-13 | Mobil Oil Corporation | V-P-Zr Catalysts and method of preparation thereof in the absence of hydrogen halide |
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