CN1453071A - Loaded V-P-O catalyst and its prepn and use - Google Patents
Loaded V-P-O catalyst and its prepn and use Download PDFInfo
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- CN1453071A CN1453071A CN 03131515 CN03131515A CN1453071A CN 1453071 A CN1453071 A CN 1453071A CN 03131515 CN03131515 CN 03131515 CN 03131515 A CN03131515 A CN 03131515A CN 1453071 A CN1453071 A CN 1453071A
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- phenylcarbinol
- isopropylcarbinol
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Abstract
The catalyst consists of loaded vanadium and phosphor oxide and SiO2 carrier formed via pyrogenic decomposition with the loaded amount being 15-58 wt%. It has a V/P atom ratio of 1.2, specific area 117-210 sq m/g, and the main phase being vanadyl pyrophosphate phase. It is used as the catalyst for air oxidizing n-butane to prepare cis-butenedioic anhydride and has one single-path conversion rate of 33-51 % and cis-butenedioic anhydride selectivity of 61-87 % in the typical temperature range of 380-400 deg.c.
Description
One, technical field
The present invention relates to the load-type vanadium phosphorus oxide catalyst and on such catalyzer, prepare MALEIC ANHYDRIDE with the air catalytic oxidation normal butane.
Two, technical background
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, lubricating oil additive, nearly hundred kinds of downstream fine-chemical intermediates such as thermal resistant styrene resin and specialty chemicals also are that production high added value fine chemicals is as 1 simultaneously, the 4-butyleneglycol, tetrahydrofuran (THF), the raw material of gamma-butyrolactone etc., its range of application is also constantly enlarging [referring to Catal.Rev.-Sci.Eng. at present, 27 (1985) 373 and Chem.Rev., 88 (1988) 50].
The early stage production of cis-butenedioic anhydride is to utilize V always
2O
5-MoO
3The selective oxidation preparation of catalyzer by benzene.Once developing afterwards with the 1-butylene is the production technique of raw material, but original V
2O
5-MoO
3Catalyzer is to the catalytic activity of 1-butylene reaction system not satisfactory [referring to Hydrocarbon Process, 11 (1980) 149].The someone found vanadium composite phosphorus oxide catalysis normal butane selective oxidation generation cis-butenedioic anhydride [US Patent 3 293268 (1966)] effectively afterwards.But therefore the resource of butane seldom should reaction not have competitive industrial at that time.Subsequently because a large amount of exploitations of Sweet natural gas make butane have abundant source and price day by day cheap.In addition, from point of view of environment protection, compare with previous benzene method production technique, the butane oxidation route also has obvious superiority.Therefore American-European developed country progressively stops benzene production route, and 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 technique of cis-butenedioic anhydride is still relatively backward, also adopts the benzene method to produce route basically, and small scale, yields poorly.Along with the fast-developing of Chinese national economy and to the obvious increase of cis-butenedioic anhydride demand, the dirt production art that changes original backwardness is imperative.Therefore, strengthen the science and technology research of this respect and to develop the achievement with independent intellectual property right significant.
For the reaction of catalysis butane Selective Oxidation cis-butenedioic anhydride, people attempted the catalyzer 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, and its main component is Vanadyl pyrophosphate ((VO)
2P
2O
7).With respect to non-carried catalyst, loaded catalyst has some advantages: the surface area/volume ratio that 1. can improve active phase (active constituent); 2. can improve the physical strength of catalyzer usually; 3. can improve the hot mass transfer of catalyzer.For this reason, existing many investigators attempt preparing the catalyzer of loading type, and used carrier comprises SiO
2, TiO
2, Al
2O
3Deng, lose sense be the performance of all these loaded catalysts that make 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].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 cause 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 on the carrier that can be reduced (as TiO
2, ZrO
2), it and carrier interactions are stronger, and also easier being reduced itself, so its catalytic activity is significantly improved, but selectivity reduces clearly; 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, selectivity of catalyst was improved but active decline.On the other hand, result of study shows also that when with water immersion process for preparing loading type vpo catalyst the more V of containing is arranged in the sample
5+Phosphoric acid salt, 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 common SiO
2Its butanes conversion of supported V PO catalyzer 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 preparation method may be also very crucial to the performance that improves the loading type vpo catalyst.
Three, summary of the invention
The purpose of this invention is to provide the better loading type vpo catalyst of a kind of performance.
Technical scheme of the present invention is as follows:
A kind of load-type vanadium phosphor oxide catalyst, it is made of loaded vanadium-phosphor oxidation thing and pyrogenic silica carrier, and charge capacity is 15～58wt%, and wherein the atomic ratio of phosphorus and vanadium is 1.2, and specific surface area is 117-210m
2/ g, the main thing of loaded vanadium-phosphor oxidation thing are the Vanadyl pyrophosphate phase mutually.
The preparation of loaded vanadium-phosphor oxide catalyst of the present invention is made up of the following step:
1. Vanadium Pentoxide in FLAKES is mixed with isopropylcarbinol-phenylcarbinol mixed solvent, during reflux 5,
2. add a certain amount of polyoxyethylene glycol, add an amount of Fumed SiO again
2Carrier, it is little to continue backflow 1
The time,
3. adding phosphoric acid, the add-on of phosphoric acid are 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),
4. continue to reflux 6 hours, have shallow orchid to blue look precipitation to separate out gradually,
5. reaction solution is cooled to room temperature, left standstill 5-10 hour, filter, with the washing with acetone filtrate for several times,
6. filtrate is warming up to 120 ℃ of dryings in air atmosphere, promptly gets load-type vanadium phosphor oxide catalyst of the present invention
Precursor, 400 ℃ of activation down in reaction mixture gas get fresh load-type vanadium of the present invention before using
Phosphor oxide catalyst.
In the above-mentioned steps 1, isopropylcarbinol-phenylcarbinol mixed solvent is made up of the isopropylcarbinol of 1-1.2 part volume and the phenylcarbinol mixing of 1 part of volume.
In the above-mentioned steps 1, the ratio of Vanadium Pentoxide in FLAKES quality and isopropylcarbinol-phenylcarbinol mixed solvent consumption is 1 gram: 22-35ml.
The polyoxyethylene glycol that adds in the above-mentioned steps 2 is that molecular weight is the polyoxyethylene glycol of 2000-20000 scope, and adding the amount of polyoxyethylene glycol and the mass ratio of Vanadium Pentoxide in FLAKES is 0.35～0.71.
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 atmospheric oxidation normal butane.The specific surface area of load-type vanadium phosphor oxide catalyst of the present invention is at 117-210m
2/ g scope, the main crystalline phase of load component is the Vanadyl pyrophosphate phase, transmission electron microscope observing finds that the vanadium phosphorus oxide particle of load is less and it is more even to distribute, even when the high capacity amount, the load particle is not significantly reunited, the See Figure photo.Method for preparing catalyst is simple and easy to do, suitable batch production.When being applied to the normal butane atmospheric oxidation and preparing cis-butenedioic anhydride, 380-400 ℃ type reaction temperature range, its per pass conversion is 33-51%, and the cis-butenedioic anhydride selectivity is 61-87%.
Characteristics of the present invention are: 1. adopt pyrogenic silica, i.e. Fumed SiO
2, as solid support material.Pyrogenic silica is a kind of special SiO
2, it does not have the one-level microvoid structure, but has bigger second hole gap structure, such SiO
2Surface-area bigger, at 250m
2About/g, suitable as solid support material; 2. adopt that co-deposition method prepares supported catalyst in organic phase, can avoid generating the more V that contains
5+Phosphoric acid salt; 3. add larger molecular organics in preparation in the medium, make the particle of loaded vanadium-phosphor oxide less and be evenly distributed; The selectivity that still can keep very high generation cis-butenedioic anhydride when 4. catalyzer has better catalytic activity.
Four, description of drawings
Fig. 1 and Fig. 2 are the stereoscan photograph of catalyzer.
Five, embodiment
Embodiment 1
Take by weighing V
2O
50.55 restrain, place the mixed solution of isopropylcarbinol/phenylcarbinol (6.1ml/6.1ml), 140 ℃ of backflows are after 5 hours, and the adding molecular weight is 2000 polyoxyethylene glycol (PEG2000) 0.26 gram, adds Fumed SiO
2Carrier 5.24 grams continue to reflux 1 hour, press the P/V=1.2/1.0 atomic ratio, adopt the mode that drips to add 85%H
3PO
40.5ml.Continue to reflux 6 hours.Filtration, drying, De Lanse throw out, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 20-40 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) in 400 ℃ of in-situ activations 12 hours, obtain the activatory live catalyst, specific surface area of catalyst is 206m
2/ g.
Take by weighing activated live catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm carries out catalytic performance test.In temperature of reaction 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), reaction mixture gas is through online gas chromatographic analysis, and its n-butane conversion is 28.1%, and the cis-butenedioic anhydride selectivity is 77.9%, and yield of maleic anhydride is 21.9%.Embodiment 2: take by weighing V
2O
51.11 restrain, place the mixed solution of isopropylcarbinol/phenylcarbinol (12.2ml/12.2ml), 140 ℃ of backflows are after 5 hours, and the adding molecular weight is 2000 polyoxyethylene glycol (PEG2000) 0.52 gram, adds Fumed SiO
2Carrier 4.86 grams continue to reflux 1 hour, press the P/V=1.2/1.0 atomic ratio, adopt the mode that drips to add 85%H
3PO
41.0ml.Continue to reflux 6 hours.Filtration, drying, De Lanse throw out, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 20-40 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) in 400 ℃ of in-situ activations 12 hours, obtain the activatory live catalyst, specific surface area of catalyst is 178m
2/ g.
Take by weighing activated live catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm carries out catalytic performance test.In temperature of reaction 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 38.3%, and the cis-butenedioic anhydride selectivity is 71.3%, and yield of maleic anhydride is 27.3%.Embodiment 3: take by weighing V
2O
51.60 restrain, place the mixed solution of isopropylcarbinol/phenylcarbinol (30.0ml/25.0ml), 140 ℃ of backflows are after 5 hours, and the adding molecular weight is 2000 polyoxyethylene glycol (PEG2000) 0.75 gram, adds Fumed SiO
2Carrier 2.00 grams continue to reflux 1 hour, press the P/V=1.2/1.0 atomic ratio, adopt the mode that drips to add 85% H
3PO
41.44ml.Continue to reflux 6 hours.Filtration, drying, De Lanse throw out, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 20-40 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) in 400 ℃ of in-situ activations 12 hours, obtain the activatory live catalyst, specific surface area of catalyst is 117m
2/ g.
Take by weighing activated live catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm carries out catalytic performance test.In temperature of reaction 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 33.0%, and the cis-butenedioic anhydride selectivity is 87.5%, and yield of maleic anhydride is 28.8%.Embodiment 4: take by weighing V
2O
50.55 restrain, place the mixed solution of isopropylcarbinol/phenylcarbinol (6.1ml/6.1ml), 140 ℃ of backflows are after 5 hours, and the adding molecular weight is 6000 polyoxyethylene glycol (PEG6000) 0.19 gram, adds FumedSiO
2Carrier 5.24 grams continue to reflux 1 hour, press the P/V=1.2/1.0 atomic ratio, adopt the mode that drips to add 85% H
3PO
40.5ml.Continue to reflux 6 hours.Filtration, drying, De Lanse throw out, 120 ℃ of air dryings.The catalyst precursor powder that makes is pressed into sheet under 0.5MPa pressure, fragmentation, sieve is got 20-40 order particulate samples and (C in reaction atmosphere
4H
10/ O
2/ N
2=1.5/17.2/81.3) in 400 ℃ of in-situ activations 12 hours, obtain the activatory live catalyst, specific surface area of catalyst is 210m
2/ g.
Take by weighing activated live catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm carries out catalytic performance test.In temperature of reaction 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 41.0%, and the cis-butenedioic anhydride selectivity is 65.0%, and yield of maleic anhydride is 26.7%.Embodiment 5: take by weighing V
2O
51.11 restrain, place the mixed solution of isopropylcarbinol/phenylcarbinol (12.2ml/12.2ml), 140 ℃ of backflows are after 5 hours, and the adding molecular weight is 20000 polyoxyethylene glycol (PEG20000) 0.67 gram, adds Fumed SiO
2Carrier 4.86 grams continue to reflux 1 hour, press the P/V=1.2/1.0 atomic ratio, adopt the mode that drips to add 85% H
3PO
41.0ml.Continue to reflux 6 hours.Filtration, drying, De Lanse throw out, 120 ℃ of air dryings.The blue look precursor (C in reaction atmosphere that more than obtains
4H
10/ O
2/ N
2=1.5/17.2/81.3) in 400 ℃ of in-situ activations 12 hours, obtain the activatory live catalyst, specific surface area of catalyst is 185m
2/ g.
Take by weighing activated live catalyst 0.5 gram, placing internal diameter is that the crystal reaction tube of 0.8cm carries out catalytic performance test.In temperature of reaction 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 50.8%, and the cis-butenedioic anhydride selectivity is 61.2%, and yield of maleic anhydride is 31.1%.
Claims (7)
1, a kind of load-type vanadium phosphor oxide catalyst is characterized in that it is made of loaded vanadium-phosphor oxidation thing and pyrogenic silica carrier, and charge capacity is counted 15-58wt% with Vanadyl pyrophosphate, and wherein the atomic ratio of phosphorus and vanadium is 1.2, and specific surface area is 117-210m
2/ g, the main thing of loaded vanadium-phosphor oxidation thing are the Vanadyl pyrophosphate phase mutually.
2, plant the method for preparing the described load-type vanadium phosphor oxide catalyst of claim 1, it is characterized in that forming by the following step:
(1) Vanadium Pentoxide in FLAKES is mixed with isopropylcarbinol-phenylcarbinol mixed solvent, during reflux 5,
(2) add a certain amount of polyoxyethylene glycol, add Fumed SiO again
2Carrier continues to reflux 1 hour,
(3) add phosphoric acid, the add-on of phosphoric acid is that to make the atomic ratio of phosphorus and vanadium be 1.2: 1.0,
(4) continue to reflux 6 hours, have shallow orchid to blue look precipitation to separate out gradually,
(5) reaction solution is cooled to room temperature, left standstill 5-10 hour, filter, with the washing with acetone filtrate for several times,
(6) filtrate is warming up to 120 ℃ of dryings in air atmosphere, promptly gets load-type vanadium phosphorus oxygen of the present invention catalysis
The agent precursor, 400 ℃ of activation down in reaction mixture gas get fresh loading type of the present invention before using
Vanadium-phosphor oxide catalyst.
3, method according to claim 2 is characterized in that in step 1, and isopropylcarbinol-phenylcarbinol mixed solvent is made up of the isopropylcarbinol of 1-1.2 part volume and the phenylcarbinol mixing of 1 part of volume.
4, method according to claim 2, the ratio that it is characterized in that Vanadium Pentoxide in FLAKES quality and isopropylcarbinol-phenylcarbinol mixed solvent consumption are 1 gram: 22-35ml.
5, method according to claim 2 is characterized in that the polyoxyethylene glycol that adds is that molecular weight is the polyoxyethylene glycol of 2000-20000 scope in step 2.
6, method according to claim 2 is characterized in that adding the amount of polyoxyethylene glycol in step 2 and the mass ratio of Vanadium Pentoxide in FLAKES is 0.35～0.71.
7, the purposes of the described catalyzer of a kind of claim 1 is characterized in that as normal butane atmospheric oxidation prepares the catalyzer of MALEIC ANHYDRIDE.
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|---|---|---|---|
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Cited By (12)
| 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 |
| CN103769182A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Supported-type vanadium-phosphorus oxide, and preparation method and applications thereof |
| CN103949277A (en) * | 2014-05-21 | 2014-07-30 | 厦门大学 | Supported vanadyl pyrophosphate catalyst prepared by selective oxidation of n-butane and preparation method thereof |
| CN104549394A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide catalyst and preparation method thereof |
| CN104607221A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide and preparation method thereof |
| CN106140125A (en) * | 2015-04-24 | 2016-11-23 | 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 |
| CN106140235A (en) * | 2015-04-24 | 2016-11-23 | 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 |
| CN104549391B (en) * | 2013-10-22 | 2017-01-11 | 中国石油化工股份有限公司 | Supported type vanadium phosphorus oxide catalyst and preparation method thereof |
| CN104549393B (en) * | 2013-10-22 | 2017-01-25 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide and preparation method thereof |
| CN106492862A (en) * | 2015-09-08 | 2017-03-15 | 中国石油化工股份有限公司 | A kind of for preparing catalyst of cis-butenedioic anhydride and preparation method thereof |
| CN106540729A (en) * | 2016-11-07 | 2017-03-29 | 山东齐鲁科力化工研究院有限公司 | Loaded catalyst and application thereof |
| CN109046413A (en) * | 2018-08-23 | 2018-12-21 | 常州新日催化剂有限公司 | One kind is for catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof |
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2003
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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 |
| CN103769182A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Supported-type vanadium-phosphorus oxide, and preparation method and applications thereof |
| CN103769182B (en) * | 2012-10-24 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of load-type vanadium phosphorous oxides and its production and use |
| CN104549394B (en) * | 2013-10-22 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of vanadium-phosphor oxide catalyst and preparation method thereof |
| CN104549394A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide catalyst and preparation method thereof |
| CN104549393B (en) * | 2013-10-22 | 2017-01-25 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide and preparation method thereof |
| CN104549391B (en) * | 2013-10-22 | 2017-01-11 | 中国石油化工股份有限公司 | Supported type vanadium phosphorus oxide catalyst and preparation method thereof |
| 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 |
| CN104607221A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Vanadium-phosphorus oxide 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 |
| CN103949277A (en) * | 2014-05-21 | 2014-07-30 | 厦门大学 | Supported vanadyl pyrophosphate catalyst prepared by selective oxidation of n-butane and preparation method thereof |
| CN106140125A (en) * | 2015-04-24 | 2016-11-23 | 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 |
| CN106140235A (en) * | 2015-04-24 | 2016-11-23 | 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 |
| 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 |
| CN106492862A (en) * | 2015-09-08 | 2017-03-15 | 中国石油化工股份有限公司 | A kind of for preparing catalyst of cis-butenedioic anhydride 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 |
| CN106540729A (en) * | 2016-11-07 | 2017-03-29 | 山东齐鲁科力化工研究院有限公司 | Loaded catalyst and application thereof |
| CN109046413A (en) * | 2018-08-23 | 2018-12-21 | 常州新日催化剂有限公司 | One kind is for catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof |
| 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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| Publication number | Publication date |
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| CN1212893C (en) | 2005-08-03 |
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