CN102989494A - Special benzene-oxidation gas phase fixed-bed catalyst for fumaric acid - Google Patents
Special benzene-oxidation gas phase fixed-bed catalyst for fumaric acid Download PDFInfo
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- CN102989494A CN102989494A CN201210575259XA CN201210575259A CN102989494A CN 102989494 A CN102989494 A CN 102989494A CN 201210575259X A CN201210575259X A CN 201210575259XA CN 201210575259 A CN201210575259 A CN 201210575259A CN 102989494 A CN102989494 A CN 102989494A
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Abstract
The invention relates to a special benzene-oxidation gas phase fixed-bed catalyst for fumaric acid. The active phase composition of the catalyst is as follows based on 1 mol of V2O5: 0.35-0.75 mol of MoO3, 0.0075-0.055 mol of P2O5, 0.005-0.100 mol of Na2O, 0.005-0.500 mol of Nio, and 0.0002-0.0012 mol of Re2O3, wherein Re is any three of Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; the carrier for the catalyst is industrial green silicon carbide; and the catalyst adopts an external activating process after the spraying process is finished. The special benzene-oxidation gas phase fixed-bed catalyst for the fumaric acid has the advantages that the activity of the catalyst is high, the benzene conversation rate in the single-tube experiment is 98.5-99%, the benzene conversation rate of the 10000 tons/year industrial device is 98.5-99.5%, the color of the produced tiglic acid aqueous solution is light, and an active carbon de-coloring process is not needed in an isomerization process of the tiglic acid. Moreover, the pure benzene can be consumed by 960-970 kilograms/ton, which is 50 kilograms or more lower than the common benzene, and so the production cost is reduced.
Description
Technical field
The present invention relates to catalyst field, the benzene oxic gas that especially relates to a kind of fumaric acid special use fixes bed catalyst.
Background technology
Fix a catalytic oxidation take benzene as unstripped gas and make abroad existing more than 80 year history of maleic anhydride, the history in more than 50 year is also arranged at home.The catalyst that adopts is vanadium molybdenum oxygen solid catalyst, because the difference of active matter prescription, carrier, preparation technology and the using method used has been delivered the patent of enormous amount, is not specifically designed to the catalyst of producing fumaric acid at all.And for the production of the most selectivity of attention of the catalyst of cis-butenedioic anhydride, and ignore activity, and cause maleic acid aqueous solution color and luster partially dark, in producing the fumaric acid process, have to add proper amount of active carbon in order to improve the color and luster of fumaric acid.
In existing a large amount of benzene method maleic anhydride catalyst, in for the manufacture of the fumaric acid process, all must add to the suitable aqueous acid that oxidation generates the active carbon more than 2%, a refining bleaching process namely is set, like this product quality of guarantee fumaric acid.
Summary of the invention
The benzene oxic gas that the invention provides a kind of fumaric acid special use fixes bed catalyst, and the more existing catalyst of this catalyst has higher activity.
For realizing above-mentioned goal of the invention, the embodiment that the present invention takes is as follows:
A kind of benzene oxic gas of fumaric acid special use fixes bed catalyst, and this active phase constitutes: with 1mol V
2O
5During for benchmark, the ratio of remaining oxide is: the MoO of 0.35～0.75mol
3, 0.0075～0.055mol P
2O
5, 0.005～0.100mol Na
2The NiO of O, 0.005～0.500mol, and the Re of 0.0002～0.0012mol
2O
3, wherein Re is among Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or the Lu any three kinds.
This catalyst used carrier is industrial carborundum.
Described industrial carborundum is the hollow cylinder structure, and it is of a size of external diameter is 5.0～6.0mm, and internal diameter is 3.0～3.5mm, height 3.5～4.0mm.
Described catalyst adopts activating process outside the device after finishing spraying coating process.
The outer activation step of described device is: place a plurality of miniature solid phase reactors in activation furnace, in this miniature solid phase reactor, finish outside the device and activate, it is in because catalyst self decomposes in the middle of the reducing atmosphere of the ammonia formation that produces, the empty ratio of ammonia is greatly about 1:10 in the controller, make in 4 hours that temperature is raised to 450～470 ℃ in the stove, be incubated 1～3 hour, naturally cool to again normal temperature.
The industrial Carboround that uses in catalyst of the present invention is characterized in that rough surface for what manually prepare, the inner almost green silicon carbide hollow circuit cylinder ring of atresia.It is industrial green silicon carbide powder take certain order number as skeleton particle, take low pressure china clay as permanent binding agent, take methylcellulose or corn flour or Ludox as interim binding agent, through extrusion molding, drying, high-temperature roasting forms.Compare with the carrier that has now, increased SR, increased reaction contact time, thereby be conducive to the raising of benzene conversion ratio.
Rationale of the present invention: in catalyst activity component prescription of the present invention, adjusted P
2O
5Ratio, make like this soda acid active sites minimizing in the active phase, and suitably increase the ratio of rare earth oxide, increased the ability of catalyst supplied for electronic, and be conducive to the suitable increase of redox active position, and integrating, the activity of catalyst will suitably improve, in addition, reduce the outside dimension of carrier, can increase bed resistance, reactant residence time is prolonged, the dividing potential drop of oxygen also can increase in reacting gas, so also can improve the activity of catalyst, namely increase the benzene conversion ratio, reduce intermediate product and the higher boiling tarry accessory substance of reaction, the final color and luster of adjusting the suitable aqueous acid of product, and then can be without the decolorizer active carbon.
The invention has the beneficial effects as follows:
The invention belongs to and be specifically designed to the benzene method fixed bed maleic anhydride catalyst of producing fumaric acid.Its advantage is that catalyst activity is high, and the benzene conversion ratio is all higher than plain edition maleic anhydride catalyst and the high yield maleic anhydride catalyst of high load capacity; 98.5～99%, 10000 ton/years of commercial plant benzene conversion ratios of single column run benzene conversion ratio are 98.5～99.5%.The suitable aqueous acid color and luster of producing is more shallow, is faint yellow or water white transparency generally speaking; Along in the acid isomer process activated carbon decolorizing operation needn't be set; Particularly importantly the purified petroleum benzin consumption of fumaric acid can reach 960～970 kg/tonnes, makes 1020～1030 kg/tonnes of fumaric acid benzene consumptions than plain edition maleic anhydride catalyst and hangs down more than 50 kilograms, has reduced production cost.
The present invention is under the prerequisite that guarantees high load capacity and yield, can also improve the color and luster of the maleic acid aqueous solution, make it cut down activated carbon decolorizing technique in the process of producing fumaric acid, process is oversimplified, also corresponding minimizing active carbon is taken away the loss of a small amount of maleic acid.We suitably adjust P in the active matter prescription for this reason
2O
5Ratio, suitably improve rare earth oxide Re
2O
3Ratio, simultaneously again the size decreases of Carboround some, can suitably improve like this activity of catalyst, the maleic acid aqueous solution color and luster of generation is shoaled, and in producing the fumaric acid process, needn't add again the decolorizer activated carbon, special suitable aqueous acid refining step namely needn't be set, the suitable aqueous acid of oxidation operation absorption tower gained directly can be added isomerization catalyst, such as ammonium persulfate, bromide and thiocarbamide etc. directly enter the isomerization operation, and suitable acid just isomery generates fumaric acid, through the crystalline deposit dehydration, dry and then obtain the finished product fumaric acid.
Use in the Catalyst Production fumaric acid process of the present invention, the yield that changes into fumaric acid by suitable acid isomer is 94～95%, the benzene consumption of fumaric acid is 960～970 kilograms of benzene/ton fumaric acid, and when using common maleic anhydride catalyst, because oxidization-hydrogenation ratio is 90%, the isomerization yield is 92%, and at this moment fumaric acid benzene consumption is at least 1020 kilograms of benzene/ton fumaric acid.Namely use the high yield TH of high load capacity series maleic anhydride catalyst, its oxidization-hydrogenation ratio can reach more than 93%, because the isomerization yield is 92%, so the benzene of fumaric acid consumption also is 990 kilograms of benzene/more than the ton fumaric acid.Catalyst of the present invention uses at 10000 ton/years of devices of the brilliant source chemical company of Northern Huaihe River Anhui, its fumaric acid benzene consumption in the lifetime of catalyst always about 970 kilograms.
The specific embodiment
Below in conjunction with embodiment, to details are as follows according to the specific embodiment provided by the invention:
Embodiment 1
1. carrier preparation
Carrier preparation of the present invention is according to patent of invention ZL200810053455.4 embodiment 1 described the carrying out before us.But catalyst size is external diameter 5.5mm internal diameter 3.5mm height 4.0mm.
2. active matter solution preparation
83.23 gram industrial ethanedioic acids are dissolved in the qualified distilled water of 380ml at normal temperature and under constantly stirring, add 78.6 gram ammonium metavanadates again, while stirring heating is until solids all dissolves.And then add 37.7 gram ammonium paramolybdates and be dissolved in the solution that 62ml distilled water generates.Under constantly stirring, add successively again tertiary sodium phosphate 5.86 grams, nickel nitrate 1.103 grams, metal dysprosium, neodymium, each 0.0692 gram of holmium, obtain at last blackish green active matter solution.
3. the preparation of catalyst
At first 280 grams are put into a rotatable heatable stainless steel rotary drum by the carrier of above-mentioned 1 method manufacturing, constantly rotating under the continuous heating condition, will be sprayed onto on the carrier surface that constantly moves in the rotary drum by a spray gun by the active matter solution of above-mentioned 2 steps preparation.320 ± 5 ℃ of spraying temperatures, rotary drum revolution 10～50rpm, spray time 50～130min.After active matter solution has sprayed, in pot, stop 1～5min, take the dish out of the pot, weigh, obtain blackish green solid catalyst 338 grams, gained catalyst activity thing content 17.2%.
4. catalyst activation
Get as stated above the catalyst 200ml of preparation, pack in the special miniature solid phase reactor, carefully seal loam cake, accomplish that the ammonia that the catalyst decomposes produces can not overflow immediately.Again above-mentioned miniature solid phase reactor is put into the high-temperature electric resistance furnace that a laboratory uses, ammonia is empty than greatly about 1:10 in the controller, makes in 4 hours that temperature is raised to 450～470 ℃ in the stove, is incubated 1～3 hour, naturally cools to normal temperature again.
5. evaluating catalyst
Get by the good catalyst 120ml of preceding method 4 activation and pack one into
Integral fixedbed reactor in.This reactor is placed in the molten salt bath.At 350～360 ℃ of salt temperature, air speed 2000～2500h
-1, benzene concentration 45～60 grams/rice
3Condition under carry out oxidation reaction.Reaction generates gas through a miniature absorption tower, it is generated along aqueous acid, when reaching 20% when above along acid concentration, taking-up solution is in an isomerization glass container, add ammonium persulfate and sodium bromide in 2% left and right sides ratio, be heated to 80～90 ℃, keep 10min under constantly stirring, leave standstill then suction filtration of 1hr, oven dry can get the finished product fumaric acid.The benzene conversion ratio is 98.5～99.5% in above-mentioned course of reaction, and the cis-butenedioic anhydride mass yield is more than 93%, and the mass yield that the cis-butenedioic anhydride isomery turns to fumaric acid is 94～95%, and the benzene consumption of fumaric acid is 960～970 kg/ton.
Embodiment 2
1. carrier preparation
Prepare carrier by embodiment 1 method 1 commercial scale, gained carrier bulk density is 0.78～0.80g/ml, specific surface (BET method) 0.15～0.2m
2/ g, press tyrannical to 〉=2.5 kilograms/, carrier dimensions external diameter 5.3～6.0mm internal diameter 3.8～4.0mm height 4.0～4.2mm.
2. active matter solution preparation
Press method 2 preparations of embodiment 1.Oxalic acid 4672 grams (being dissolved in the 17L distilled water), ammonium metavanadate 3716 grams, ammonium paramolybdate 1947 grams (being dissolved in the 3.4L distilled water), tertiary sodium phosphate 273 grams (being dissolved in the 0.5L distilled water), nickel nitrate 78 grams (being dissolved in the 80ml distilled water), dysprosium, neodymium, each 3.990 gram of holmium.
3. catalyst preparation
Press method 3 Kaolinite Preparation of Catalysts of embodiment 1, amount vector is 17.3 kilograms.
4. catalyst activation
Catalyst by 4 pairs of above-mentioned preparations of method of embodiment 1 activates.
5. evaluating catalyst
5 pairs of above-mentioned catalyst that activated of method by embodiment 1 carry out evaluation test.The result of evaluation test is: benzene conversion ratio 98.4～99.7%, and the mass yield of cis-butenedioic anhydride is more than 95%; The mass yield that the cis-butenedioic anhydride isomery turns to fumaric acid is 94～95%, and the benzene consumption of fumaric acid is 950～960 kg/ton.
Embodiment 3
1. carrier preparation
With embodiment 2
2. active matter solution preparation
Press method 2 preparations of embodiment 1.Oxalic acid 4672 grams (being dissolved in the 17L distilled water), ammonium metavanadate 3716 grams, ammonium paramolybdate 1900 grams (being dissolved in the 3.4L distilled water), tertiary sodium phosphate 287 grams (being dissolved in the 0.45L distilled water), nickel nitrate 78 grams (being dissolved in the 80ml distilled water), dysprosium, neodymium, each 3.794 gram of holmium.
3. catalyst preparation
Press method 3 Kaolinite Preparation of Catalysts of embodiment 1, amount vector is 17.3 kilograms.
4. catalyst activation
4 pairs of above-mentioned catalyst of method by embodiment 1 activate.
5. evaluating catalyst
5 pairs of above-mentioned catalyst that activated of method by embodiment 1 carry out evaluation test.The result is: benzene conversion ratio 98.8～99.6%, and cis-butenedioic anhydride mass yield 95%, the mass yield that turns to fumaric acid along acid isomer is 94～95%, benzene consumption 950～960 kg/ton of fumaric acid.
Embodiment 4
1. carrier preparation
With embodiment 2
2. active matter solution preparation
Press method 2 preparations of embodiment 1, oxalic acid 4672 grams (being dissolved in the 17L water), ammonium metavanadate 3761 grams, ammonium paramolybdate 1900 grams (being dissolved in the 3.4L water), tertiary sodium phosphate 287 grams (being dissolved in the 0.45L water), nickel nitrate 78 grams (being dissolved in the 80ml water), dysprosium, neodymium, each 2.909 gram of holmium.
3. catalyst preparation
Press method 3 Kaolinite Preparation of Catalysts of embodiment 1,17.3 kilograms of amount vectors.
4. catalyst activation
4 pairs of above-mentioned catalyst of method by embodiment 1 activate.
5. evaluating catalyst
Estimate by the above-mentioned catalyst that 5 pairs of the methods of embodiment 1 had activated.The evaluation test result is: the benzene conversion ratio is more than 99.0%, and cis-butenedioic anhydride mass yield about 95% turns to the mass yield 94～95% of fumaric acid, benzene consumption 950～960 kg/ton of fumaric acid along acid isomer.
Embodiment 5
This example is a Large Scale Industrial Process effect case.
The industrial fumaric acid device of the brilliant source 10Kt/a of chemical industry Co., Ltd of Northern Huaihe River Anhui, this reactor diameter 5000mm has 13944 reaction tubes, pipe range 3600mm, bore 21mm, bed inner catalyst height 3200mm, 12 tons of total catalyst weight, admission space is about 15m
3Device operates steadily continuously, and lifetime is 2.5 years, and 2 batches of these catalyst have been used in front and back.
Total output industry fumaric acid is about 27000 tons in the lifetime, and the average benzene consumption of fumaric acid is 960～980 kg/ton, benzene conversion ratio 98.0～99.0%, and cis-butenedioic anhydride mass yield 90～93%, suitable acid isomer turns to the mass yield about 94% of fumaric acid.About fumaric acid product color APHA10#, device is not established the activated carbon decolorizing operation.
Embodiment 6
Following the effect list introduction of several representational industrial maleic anhydride catalysts in producing the fumaric acid process.
Several main benzene method maleic anhydride catalyst are produced performance contrast (situation before 6 months) at fumaric acid
Claims (5)
1. the benzene oxic gas of a fumaric acid special use fixes bed catalyst, it is characterized in that: this active phase constitutes: with 1mol V
2O
5During for benchmark, the ratio of remaining oxide is: the MoO of 0.35～0.75mol
3, 0.0075～0.055mol P
2O
5, 0.005～0.100mol Na
2The NiO of O, 0.005～0.500mol, and the Re of 0.0002～0.0012mol
2O
3, wherein Re is among Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or the Lu any three kinds.
2. the benzene oxic gas of fumaric acid special use according to claim 1 fixes bed catalyst, it is characterized in that: this catalyst used carrier is industrial green silicon carbide.
3. the benzene oxic gas of fumaric acid special use according to claim 2 fixes bed catalyst, it is characterized in that: described industrial green silicon carbide is the hollow circuit cylinder ring structure, and it is of a size of external diameter is 5.0～6.0mm, and internal diameter is 3.0～3.5mm, height 3.5～4.0mm.
4. the benzene oxic gas of fumaric acid special use according to claim 3 fixes bed catalyst, it is characterized in that: described catalyst adopts activating process outside the device after finishing spraying coating process.
5. the benzene oxic gas of fumaric acid special use according to claim 4 fixes bed catalyst, it is characterized in that: the outer activation step of described device is: place a plurality of miniature solid phase reactors in activation furnace, in this miniature solid phase reactor, finish outside the device and activate, it is in because catalyst self decomposes in the middle of the reducing atmosphere of the ammonia formation that produces, the empty ratio of ammonia is greatly about 1:10 in the controller, make in 4 hours that temperature is raised to 450～470 ℃ in the stove, be incubated 1～3 hour, naturally cool to again normal temperature.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118402A (en) * | 1974-12-02 | 1978-10-03 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Preparation of maleic anhydride |
| CN1579631A (en) * | 2003-08-15 | 2005-02-16 | 天津市天环精细化工研究所 | External activating method of cis-butenedioic anhydride catalyst |
| CN101284242A (en) * | 2008-06-06 | 2008-10-15 | 天津市天环精细化工研究所 | Catalyst for producing maleic anhydrid(e) by benzene gas-phase oxidation with high load and high yield |
-
2012
- 2012-12-24 CN CN201210575259XA patent/CN102989494A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118402A (en) * | 1974-12-02 | 1978-10-03 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Preparation of maleic anhydride |
| CN1579631A (en) * | 2003-08-15 | 2005-02-16 | 天津市天环精细化工研究所 | External activating method of cis-butenedioic anhydride catalyst |
| CN101284242A (en) * | 2008-06-06 | 2008-10-15 | 天津市天环精细化工研究所 | Catalyst for producing maleic anhydrid(e) by benzene gas-phase oxidation with high load and high yield |
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Application publication date: 20130327 |