CN1059297A - The method for preparing catalyst of producing maleic anhydride by n-butane oxidation with fluid bed method - Google Patents
The method for preparing catalyst of producing maleic anhydride by n-butane oxidation with fluid bed method Download PDFInfo
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- CN1059297A CN1059297A CN 91109538 CN91109538A CN1059297A CN 1059297 A CN1059297 A CN 1059297A CN 91109538 CN91109538 CN 91109538 CN 91109538 A CN91109538 A CN 91109538A CN 1059297 A CN1059297 A CN 1059297A
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Abstract
The invention provides a kind of raw material and be easy to get, inexpensive, technology is simple, good reproducibility, and the V-P-O series catalysts manufacture method of the producing maleic anhydride by n-butane oxidation with fluid bed method that environmental pollution is little is characterized in adopting the organic solvent reducing process, with the V of technical grade
2O85% phosphoric acid is raw material, is reducing agent with the technical grade isobutanol, carries out reduction reaction in having the stirred autoclave with Steam Heating chuck of destilling tower, adopt azeotropic distillation technology and hot filter technology, reaction is after the heat filter dries filter cake, and drying makes catalyst precursor.Precursor is handled through modification, adds metal promoters, and mixing is sized mixing, and spray drying forming makes the micro-spherical catalyst of producing maleic anhydride by n-butane oxidation with fluid bed method.
Description
The invention belongs to Chemical Engineering Preparation of catalysts method.
Maleic anhydride (abbreviation cis-butenedioic anhydride) is important Organic Chemicals, is used to produce thermosetting resin, unsaturated polyester resin, agricultural chemicals and fine chemical product in a large number.Early stage cis-butenedioic anhydride production is raw material with benzene, and national of the United States's aniline in 1933 and chemical company have realized the industrial production of vapor phase method benzene preparing cis-butenedioic anhydride by oxidation.Nineteen sixty, american petroleum-Texas chemical company (Petrotex Chemical conp.) set up the commercial plant that butylene oxidation is produced cis-butenedioic anhydride.Mitsubishi chemical company had at first realized the technology that the fluid-bed catalytic oxidizing C-4-fraction is produced cis-butenedioic anhydride in 1970.From the seventies, turning to gradually with normal butane substituted benzene cheap and easy to get and butylene is that raw material is produced cis-butenedioic anhydride.At present, be that the industrial route that raw material is produced cis-butenedioic anhydride is subjected to gazing at of countries in the world with the normal butane, U.S. Meng Shan in 1974 (Monsento conp.) company has realized the industrial production of preparing cis-anhydride by n-butane oxidation fixed bed process, but fluidized bed process has more advantage than fixed bed process.
Relatively think by the economy that U.S. Si Tanfu research institute (SRI) produces the different process method at the cis-butenedioic anhydride of nineteen eighty-three announcement: be that raw material ratio benzene method and butylene method are wanted economy with the normal butane, adopt fluidized bed process more reasonable than fixed bed process, calculate by 30,000 tons of/year maleic anhydride yields, the investment of normal butane fixed bed is 2,200 ten thousand dollars, and fluid bed only needs 1,400 ten thousand dollars, saves the investment cost of half approximately.
Current, the producing maleic anhydride by n-butane oxidation with fluid bed method catalyst research is paid much attention to, and develop, it and fixed bed process catalyst for preparing cis-anhydride by n-butane oxidation are different, and this catalyst at first should guarantee enough activity and intensity, the performance that has wearability and bear high concentration raw material load, Zhi Bei catalyst will have the easy-formation processing characteristics in addition, the micro-spherical catalyst of making will have the easy mobility energy, prevents the catalyst granules bonding, influences fluidization quality.Therefore, preparing cis-anhydride by n-butane oxidation fluidized bed process catalyst research is higher than the requirement of fixed bed process catalyst research, difficulty is big, is the industrialized key of fluidized bed process, has wide prospect in industrial application.
U.S.'s Mobile (Mobil) company is research producing maleic anhydride by n-butane oxidation with fluid bed method catalyst a company the earliest, delivered the research report of many fluid catalysts in succession from late nineteen seventies, enter the eighties, the said firm and U.S. shellfish get (Badger) company and have developed jointly C
4The preparing cis-butenedioic anhydride by oxidation fluidized-bed process.The catalyst characteristics of being developed are to adopt the heterogeneous reducing process of the aqueous solution, are reducing agent as spent glycol, phosphate, and add metal the 3rd component, and catalyst activity is not high, but reaction condition gentleness, for example Mobil patent report.
400 ℃ of reaction temperatures
10 seconds times of contact
Charging normal butane molar concentration 4%
Yield of maleic anhydride 83.3%(weight)
Reaction conversion ratio 81.8%
Selectivity 60%(mol%)
Catalyst space time yield 37.7g/l.h.
Unite States Standard oil product company actively develops in recent ten years, the research of producing maleic anhydride by n-butane oxidation with fluid bed method catalyst, wherein active with Sohio (Sohio), the catalyst of the said firm's development adopts organic solvent to prepare vanadium phosphorus oxygen series catalysts, be characterized in adopting highly purified anhydrous phosphoric acid or pyrophosphoric acid, the assurance raw material is anhydrous, and the catalyst precursor of generation is dispersed in the organic facies, and the catalyst activity of preparation is better.Be reported at 1.5 o'clock according to the Sohio patent and carry out the preparing cis-anhydride by n-butane oxidation reaction in the diameter stainless steel fluid bed, 400～425 ℃ of temperature, 6.7～10 seconds times of contact, it is 53.6-60%(gram molecule % that normal butane molar concentration 2.7～4.4% obtains yield of maleic anhydride), n-butane conversion is 58-70%, and catalyst has stability preferably.The said firm and Belgian Unichem (UCB) have used nearly ten years to develop the preparing cis-anhydride by n-butane oxidation fluid bed jointly, and a cover pilot-plant turns round.Mitsubishi becomes the cis-butenedioic anhydride fluid bed with the Sohio cooperation with original acrylonitrile fluid bed plant modification, production capacity is 10,000 tons/year, establish by MTC Sohio company, go into operation the end of the year 1988, it is the first batch of suitability for industrialized production of preparing cis-anhydride by n-butane oxidation fluidized bed process factory, according to reports, it is than the low 15-40% of fixed bed process cost.
Lu Musi (Lummus) company carries out the producing maleic anhydride by n-butane oxidation with fluid bed method catalyst research in recent years, and the catalyst of the said firm's development is that reduction makes vanadium phosphorus oxygen series catalysts in organic solvent.Use acid treatment to improve catalyst strength simultaneously, add a certain amount of boron, aluminium enhancing wearability, the catalyst spray shaping was made 40～200 μ microballoons, reacted 410 ℃ of temperature in the bed at 2 o'clock, normal butane molar concentration 4%, obtain cis-butenedioic anhydride molar yield 45.3-57.8%, n-butane conversion 74.8-81.8%, reaction selectivity 60.5-70%, catalyst abrasion rate 3-6% satisfies industrial requirements.
MIT has studied the producing maleic anhydride by n-butane oxidation with fluid bed method catalyst research again on the basis of fluidized bed process butylene oxidation catalyst for preparing cis-anhydride research recently, the said firm adopts hydrochloric acid or hydrazine hydrochloride to make reducing agent, carry out reduction reaction in the aqueous solution, the vanadium phosphorus catalyst of producing is highly purified vanadium phosphorus crystal.According to the patent report, lab scale is studied at temperature 410-440 ℃, air speed 500h
-1, normal butane molar concentration 1.58-4% obtains n-butane conversion 77-94%, cis-butenedioic anhydride molar yield 37.5-50.9%.Some other company such as Ai Kexun (FXXON) company, (Dupont) company etc. of Du group has all studied the producing maleic anhydride by n-butane oxidation with fluid bed method catalyst in succession.
The purpose of this invention is to provide a kind of raw material and be easy to get, inexpensive, manufacturing process is simple, good reproducibility, the preparation method of the V-P-O series catalysts of the producing maleic anhydride by n-butane oxidation with fluid bed method that environmental pollution is little.
Main points of the present invention are that employing organic solvent reducing process is a raw material with technical grade vanadic anhydride and phosphoric acid, with the technical grade isobutanol is reducing agent, having destilling tower, have in the stirred autoclave of steam heated chuck and carry out reduction reaction, adopt azeotropic distillation technology and hot filter technology, after filtration, drying makes catalyst precursor after the reaction.Precursor is handled through modification, adds metal promoters, and mixing is sized mixing, and spray drying forming makes the micro-spherical catalyst of producing maleic anhydride by n-butane oxidation with fluid bed method.
Preparation process of the present invention is shown in figure one.To behind ball milling, ground particle mean size be the technical grade V of 5nm
2O
5Powder and content are the H of 85% technical grade
3PO
4Be respectively charged in raw material measuring tank 1 and 2, with V
2O
5For benchmark is pressed V
+ 5Be reduced to V
+ 4During reaction, four times of calculating of required technical grade isobutanol (boiling range is 107～108 ℃) theoretical amount, pack into groove 3(generally speaking the weight ratio of isobutanol and vanadic anhydride be 8: 1), with the isobutanol of measuring tank 3 and the V in the measuring tank 1
2O
5Add simultaneously and have in the stainless steel stirred autoclave 7 with Steam Heating chuck of destilling tower, heat temperature raising also stirs, open the cooling water of the reflux condenser 4 of the destilling tower 6 that links to each other with the reactor top this moment, to prevent that isobutanol is because of loss on heating, when treating the still temperature near 100 ℃, begin to drip phosphoric acid from phosphoric acid measuring tank 2, the phosphoric acid charging rate is 1 liter/time～2.5 liter/time, the best be 1.5 liters/time, charging finishes, and continues to heat up, and makes the still temperature be in 107～108 ℃, constantly have this moment water deviate from and with still in isobutanol form azeotropic mixture, be to accelerate reduction rate, improve catalyst activity and stability, should be constantly the destilling tower 6 at azeotropic mixture autoreaction still top be steamed, the control reflux ratio is 0.5～1, and the speed that distillates was advisable with 0.1～0.5 liter/time.Reaction was carried out 6-12 hour continuously, and sample analysis is until V
+ 5Substantially be reduced to V
+ 4, the vanadium valence state is met the requirements till.Reduction reaction finishes, stop the heating cooling, for improving the bulk density of catalyst, activity and caking property, when 35～45 ℃ in slurries, the best is 40 ℃ and carries out heat filtering 9, dries filter cake in centrifuge 10, in drying box 11, under 110 ℃ of conditions, toasted 4～8 hours, obtain V-P-O series catalysts precursor.
The vanadium phosphorus oxygen series catalysts precursor that obtains is handled through 12 modifications, 13 add metal the 3rd component co-catalyst, 14 add adhesive sizes mixing and 15 mist projection granulating moulding, and can obtain particle diameter is 20～200nm, and average grain diameter is the microspherical catalyst of fluid bed 16 of 70～80nm.
It is that catalyst precursor is heated in the organic or inorganic solvent that modification is handled, and then removes solvent and make its crystallization again, adopts alcohol or other solvent to handle usually, and the present invention then uses cheap water as solvent, and effect is rather good; Modification is handled and can be repeated for several times.The middle mutually crystallite of modification rear catalyst activity increases mutually, and reaction selectivity is improved, and stability of catalytic activity is strengthened.
It is co-catalyst that catalyst after the modification is added trace meter the 3rd active component, to improve the catalyst activity valence state, selects IV in the periodic table of elements usually for use
BFamily, VI
BFamily, some metallic elements of VIII family are as zirconium, molybdenum, iron etc.Experiment shows, adds trace meter and can significantly improve reaction yield and selectivity, stable catalytic activity.The metal addition is a benchmark by the atom of vanadium, and is more suitable about 0.001～0.01 scope, is preferably in about 0.005 for well.Addition manner can adopt the dipping absorption method, also can adopt coprecipitation, preferably after the dry constant weight of the catalyst that modification is handled, presses the salting liquid of incipient impregnation metal.
With the catalyst powder of preparation, the admixture adhesive, the spray shaping of sizing mixing, adhesive can adopt Ludox, aluminium glue, polyvinyl alcohol etc. preferably adopt 20% Ludox, press certain proportioning of catalyst and adhesive, and add quantitative deionized water making beating, after the slurries modulation is qualified, get final product spray shaping.The spray operation condition is: atomisation pressure 0.1～0.8MPa, the spray-drying temperature is 120～160 ℃, gas-liquid mass ratio 0.01～0.1, adopt the air-flowing type nozzle, select the small-bore of 1 millimeter, atomization quality is better, and the catalyst droplet of moulding is also dehydrating in stream or the reverse-flow drying tower, make catalyst particle size in 20～200nm scope, its average grain diameter is best at the microspherical catalyst reaction effect of 70～80nm.
Fluid bed provided by the invention in realizing preparation process, removes above-mentioned process conditions with the V-P-O series catalysts of preparing cis-anhydride by n-butane oxidation, also will control following factor technically:
A: the metering of raw material proportioning is important link, because the phosphorus vanadium is the key of decision catalytic activity than (P/V) in the catalyst, P/V atomic ratio in the raw material proportioning more than 1/1 for well, the P/V atomic ratio is more suitable in 1/1～1.3/1 scope generally speaking, the best is about 1.2/1.So before feed proportioning, must be to V
2O
5In content of vanadium and the phosphorus content in the phosphoric acid detect.
B: control isobutanol proportioning, the reducing agent isobutanol is a technical grade, and boiling range is 107～108 ℃, and its consumption is pressed V
+ 5Be reduced to V
+ 4Four times of calculating of Shi Suoxu theoretical amount in the ordinary course of things, can be advisable about 8: 1 by isobutanol and vanadic anhydride weight ratio.
C: control phosphoric acid feed rate, feed rate has certain influence to the catalyst activity of preparation, particularly the reactor fluid viscosity is excessive when reinforced too fast, reduction reaction is worsened, generally when catalyst treatment reduction of feed volume during at 3～5 liters, the phosphoric acid charging rate is 1 liter/time～2.5 liter/time, the best be 1.5 liters/time, suitably adjust the phosphoric acid charging rate according to the big I for the treatment of capacity.
The fluid bed of the present invention preparation is the catalyst of preparing cis-anhydride by n-butane oxidation with V-P-O, and compares with the catalyst of system both at home and abroad, has following characteristics:
1, with the V of technical grade
2O
5And 85%H
3PO
4Be raw material, directly carry out reduction reaction, having changed to be the traditional handicraft that raw material carries out reduction reaction with pure material, and has realized the technical process of new preparation catalyst.
2, adopt the nonaqueous solvents reducing process in the preparation process, filter out the best proportioning of using reducing agent isobutanol and raw material, its value is lower than existing patent documentation index, and has avoided using the etching problem that inorganic acid brought.
3, in reduction process, adopt azeotropic distillation technology, at the reactor top destilling tower is housed, be used for constantly steaming the water and the low-boiling-point substance that generate in the course of reaction, wherein be unfavorable for reacting the water that carries out, steam with isobutanol-water azeotropic mixture form, accelerate the reaction speed of reduction process, improved activity of such catalysts and stability.
4, adopt hot filter technology, remove the repeatedly washing methods in the traditional handicraft from, and the more important thing is the spray shaping that adopts the heat filter to help fluid catalyst, improve the bulk density and the reaction selectivity of catalyst, be suitable for the fluidized-bed reaction feature.
5, be that solvent carries out the modification processing to catalyst precursor with water, the middle mutually crystallite of activity of such catalysts is increased mutually, help activity of such catalysts and optionally raising.
The optimum data contrast is as follows in the catalyst of the present invention's preparation and the patent documentation:
Embodiments of the invention are as follows:
(example 1) technical grade V
2O
5And 85%H
3PO
4Press P/V mol ratio 1.2/1 batching, with above-mentioned preparation manipulation step, make major catalyst not add metal, add 0.1% zirconates then, make Zr catalyst, if interpolation simultaneously waits the gram atom molybdenum to make zirconium, molybdenum bimetallic catalyst, in the 30mm fluid bed, carry out the preparing cis-anhydride by n-butane oxidation reaction respectively, 390～400 ℃ of operating temperatures, reaction contact time 3.6 seconds, concentration of n-butane 1.8～2.0%(mol%) reaction result such as tables 1.
(example 2) handled above-mentioned major catalyst the catalyst that obtains and flood 0.005 on the major catalyst basis through three modifications: 1(Z
r/ V gram atom ratio) Zr catalyst that metal component is made with two kinds of microspherical catalysts that make, reacts in the 54mm fluid bed, 390～400 ℃ of operating temperatures, reaction contact time 3.6 seconds, concentration of n-butane 1.8～2%(mol%), running continuously in 500 hours is carried out in reaction, reaction result such as table 2:
Can find out that from table 2 comparing result the catalyst reaction result that the interpolation metal promoters is handled than triplicate modification is good.
(example 3) is the examination catalyst stability, with above-mentioned Zr catalyst and the life experiment that carries out running in continuous 1500 hours respectively through the catalyst that three modifications are handled, and result such as table 3:
Found out after long-time running that by the result Zr catalyst is steadily active, and on the rise, recording 1500 hours rear catalyst relative wear rates is 2～5%.
Claims (7)
1, a kind of preparation method who is used for the V-P-O series catalysts of producing maleic anhydride by n-butane oxidation with fluid bed method, it is characterized in that vanadic anhydride and 85% phosphoric acid with the technical grade of certain proportioning are raw material, with the isobutanol is reducing agent, carry out reduction reaction in having the stirred autoclave with Steam Heating chuck of destilling tower, through the heat filter, modification is handled again, add metal promoters, size mixing, spray drying forming makes microspherical catalyst.
2, according to the vanadic anhydride and 85% phosphoric acid of the technical grade of the said certain proportioning of claim 1, it is characterized in that the P/V atomic ratio in the raw material proportioning is 1/1～1.3/1, optimum value is 1.2/1.
3, according to the said reducing agent isobutanol of claim 1, it is characterized in that boiling range is 107～108 ℃ a technical grade isobutanol, it is optimum that addition is reduced four times of required theoretical amount with vanadium.
4, according to the said destilling tower of claim 1, it is characterized in that using the azeotropic distillation technology fast reaction speed, and constantly steam water (steaming with the azeotropic mixture form) and the low-boiling-point substance that generates in the reaction with isobutanol.
5, according to the said heat filter of claim 1, it is characterized in that using hot filter technology, to improve the bulk density of catalyst, heat filter temperature is 35～45 ℃, and optimum temperature is 40 ℃, and bulk density can improve 0.2～0.3g/cm
3
6, said modification is handled according to claim 1, it is characterized in that with water being solvent.
7, according to the said interpolation metal promoters of claim 1, it is characterized in that with zirconium metals such as molybdenum are co-catalyst, addition is 0.001～0.01 with the atomic ratio of metal and vanadium, and optimum value is 0.005.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 91109538 CN1026297C (en) | 1991-10-17 | 1991-10-17 | Method of preparing catalyst for producing maleic anhydride by n-butane oxidation with fluid bed method |
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|---|---|---|---|
| CN 91109538 CN1026297C (en) | 1991-10-17 | 1991-10-17 | Method of preparing catalyst for producing maleic anhydride by n-butane oxidation with fluid bed method |
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| CN1059297A true CN1059297A (en) | 1992-03-11 |
| CN1026297C CN1026297C (en) | 1994-10-26 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059845C (en) * | 1996-04-25 | 2000-12-27 | 中国石油化工总公司 | Alkane oxidation catalyst and its preparing method |
| US7547655B2 (en) | 2003-01-30 | 2009-06-16 | New Tianjin T. & D. Co., Ltd. | V-P-Si composite oxide catalyst precursor used for producing maleic anhydride from butance |
| 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 |
| CN105618094A (en) * | 2016-03-21 | 2016-06-01 | 唐伟 | Preparation equipment for oxidation catalyst and process of preparation equipment |
| CN116060061A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Vanadium phosphorus oxygen catalyst precursor powder and catalyst prepared from same |
| CN116060061B (en) * | 2021-10-31 | 2024-05-31 | 中国石油化工股份有限公司 | Vanadium phosphorus oxygen catalyst precursor powder and catalyst prepared from same |
-
1991
- 1991-10-17 CN CN 91109538 patent/CN1026297C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059845C (en) * | 1996-04-25 | 2000-12-27 | 中国石油化工总公司 | Alkane oxidation catalyst and its preparing method |
| US7547655B2 (en) | 2003-01-30 | 2009-06-16 | New Tianjin T. & D. Co., Ltd. | V-P-Si composite oxide catalyst precursor used for producing maleic anhydride from butance |
| 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 |
| 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 |
| CN105618094A (en) * | 2016-03-21 | 2016-06-01 | 唐伟 | Preparation equipment for oxidation catalyst and process of preparation equipment |
| CN116060061A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Vanadium phosphorus oxygen catalyst precursor powder and catalyst prepared from same |
| CN116060061B (en) * | 2021-10-31 | 2024-05-31 | 中国石油化工股份有限公司 | Vanadium phosphorus oxygen catalyst precursor powder and catalyst prepared from same |
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| Publication number | Publication date |
|---|---|
| CN1026297C (en) | 1994-10-26 |
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