CN103028411A - Novel N-methyl aniline catalyst synthesized through chromium-free gas phase method - Google Patents
Novel N-methyl aniline catalyst synthesized through chromium-free gas phase method Download PDFInfo
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- CN103028411A CN103028411A CN2013100040729A CN201310004072A CN103028411A CN 103028411 A CN103028411 A CN 103028411A CN 2013100040729 A CN2013100040729 A CN 2013100040729A CN 201310004072 A CN201310004072 A CN 201310004072A CN 103028411 A CN103028411 A CN 103028411A
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Abstract
The invention belongs to the technical field of catalyst, and relates to a novel catalyst used for producing N-methyl aniline through the stationary bed reaction of aniline and methyl alcohol in gas phase method. The catalyst does not contain chrome, and the catalyst contains the following components by weight (accounted by oxide): 30 to 70 percent of copper, 10 to 50 percent of zinc, 5 to 20 percent of alkaline-earth metals, and 0.2 to 2 percent of rare earth element cerium or lanthanum. According to the invention, the catalyst does not contain chrome, so that not only the chrome pollution in the production process of the catalyst is reduced, but also the chrome pollution in the use process of the catalyst and down-stream products is reduced; and when N-methyl aniline is produced by using the catalyst, N,N-methyl toluidine generated in the reaction is rather low in content. The property of the catalyst can reach or surpass that of the products used in current industrial devices, the strength is high, and the conversion ratio as well as the selectivity is high. The working condition of the catalyst is that the pressure is normal pressure, the mole ratio of methyl alcohol and aniline is 1.5 to 1, and the liquid hourly space velocity is 0.6 h<-1>.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of new catalyst for aniline and methanol vapor phase method fixed bed reaction production methylphenylamine.Do not contain chromium in the catalyst, both reduced the pollution of chromium in the Catalyst Production, reduced again the pollution of chromium in catalyst use procedure and the downstream product; During with this Catalyst Production methylphenylamine, cross the N that reaction forms, N one dimethyl benzene amine content is extremely low.
Background technology
Utilizing the calandria type fixed bed reactor vapor phase method to produce methylphenylamine is a kind of ripe advanced technique, domestic existing nearly 30 years history, the catalyst that uses on the domestic industry device at present is copper, zinc, the cylindrical compressing tablet catalyst of chromium, and stable performance uses widely that model has CNW-1 and QC-5 etc.
Chromium element in the copper zinc chrome plays carrier and heat-staple effect, but chromium is a kind of environmentally harmful metallic element.Not only in Catalyst Production, there is pollution of chromium, and in catalyst use procedure and downstream product, also has the problem of pollution of chromium.
Summary of the invention
The objective of the invention is to propose a kind of new catalyst for aniline and methanol vapor phase method fixed bed reaction production methylphenylamine.Replace chromium with complex carrier, prepared all good new catalysts of Chrome-free and activity and selectivity.
Major programme of the present invention: novel Chrome-free vapor phase method synthesizes the methylphenylamine catalyst, be used for aniline and methanol vapor phase method fixed bed reaction and produce methylphenylamine, it is characterized in that not containing in the catalyst chromium, catalyst contains the copper of weight (in oxide) 30% ~ 70%, 10% ~ 50% zinc, 5% ~ 20% alkaline-earth metal, 0.2% ~ 2% rare-earth element cerium or lanthanum.
Normally, described alkaline-earth metal is one or both in calcium, magnesium, the barium.
The preferred scheme of catalyst of the present invention: catalyst contains the copper of weight (in oxide) 30% ~ 60%, 15% ~ 45% zinc, 5% ~ 18% alkaline-earth metal, 0.5% ~ 2% rare-earth element cerium or lanthanum; Optimal case: catalyst contains copper, 15% ~ 45% zinc, 5% ~ 15% magnesium and the barium of weight (in oxide) 30% ~ 50%, 0.5% ~ 1.8% rare-earth element cerium or lanthanum.
Usually, catalyst of the present invention adopts the coprecipitation preparation, the concrete technology flow process is: with a certain proportion of copper nitrate, zinc nitrate, magnesium nitrate, barium nitrate and cerous nitrate or lanthanum nitrate water dissolve to get nitrate mixed solution, with hot water preparation sodium carbonate liquor or sodium bicarbonate aqueous solution, then nitrate solution is added (or in sodium bicarbonate solution) in the sodium carbonate liquor, also can be with sodium carbonate liquor (or sodium bicarbonate solution), add nitrate mixed solution, after reacting to terminal pH=6.0-8.5, filter material, sodium ion in the flush away material, then oven dry, and 320-450 ℃ of lower roasting, add afterwards suitable quantity of water and graphite, with the tablet of rotary tablet machine compacting Ф 5 * (4.5-5.5) mm.Need before the catalyst use namely in nitrogen, to prepare certain density hydrogen through the step of reduction, heat up stage by stage, do not go out till the reductive water until do not consume hydrogen.
Catalyst of the present invention does not contain chromium, and catalyst performance reaches and surpasses the properties of product that present commercial plant uses, and intensity is high, conversion ratio and selective high.The catalyst service condition: pressure is normal pressure, methyl alcohol and aniline mol ratio 1.5:1, liquid air speed 0.6h
-1
The specific embodiment
Below in conjunction with embodiment the present invention is described in detail.
Slaine among following comparative example and the embodiment is nitrate trihydrate copper and zinc nitrate hexahydrate and six water cerous nitrates, and magnesium nitrate hexahydrate and barium nitrate.
Comparative example 1:
The catalyst that is used for aniline and methanol vapor phase method fixed bed reaction production methylphenylamine of present industrial application, main component is copper, zinc, chromium.Be of a size of Ф 5 * (4.5-5.5) mm.
Comparative example 2: the catalyst that is used for aniline and methanol vapor phase method fixed bed reaction production methylphenylamine that the applicant produced in the past.
With 256.7 kilograms Gerhardite, 178.5 kilograms zinc nitrate hexahydrate, 72.8 kilograms Chromium nitrate (Cr(NO3)3),nonahydrate are poured the allotment bucket into, add water again and make 1.5 cubic metres mixed liquor A; The natrium carbonicum calcinatum that in settling box, adds in addition 180 kilograms, the alkali lye B that is made into 3 cubic metres and be heated to 70 degree is dissolved in water; Then mixed liquor A is slowly splashed among the alkali lye B, until add.Then filtration washing, and dry under 100 degree, and the material that obtains adds the graphite moulding, the finished catalyst of system.This catalyst (in oxide) copper 40.3%, zinc 23.2% contains chromium 7.3%.
Embodiment 1: with the 365g copper nitrate, the 392g zinc nitrate, 47.8g magnesium nitrate, 21.3g the cerous nitrate of barium nitrate and 6.3g is dissolved in the 1L water, be heated to 50 ℃, the 650g sodium acid carbonate is dissolved in the 3L water, and be heated to 70 ℃, then sodium bicarbonate solution is slowly dropped in the mixed solution of nitrate, the while rapid stirring, stirred 1 hour until pH=7.5. is warmed up to 80 ℃ again, follow filtration washing, solid material was 120 ℃ of lower oven dry 6 hours, 300 ℃ of lower roastings 2 hours, then add 2% graphite and 4% water and mix, be pressed into the tablet of Ф 5 * (4.5-5.5) mm, the Components of Catalysts that makes like this (in oxide) 48% bronze medal with tablet press machine, 43% zinc, 3% magnesium, 5% barium, 1.% cerium.
Embodiment 2:
With the 350g copper nitrate, the 338g zinc nitrate, the 143g magnesium nitrate, 27.7g barium nitrate and 9.5g cerous nitrate are dissolved in the 1L water, be heated to 50 ℃, 500g sodium carbonate is dissolved in the 3L water, and be heated to 70 ℃, then sodium carbonate is slowly dropped in the mixed solution of nitrate, the while rapid stirring, stirred 1 hour until pH=7.5. is warmed up to 80 ℃ again, follow filtration washing, solid material was 120 ℃ of lower oven dry 6 hours, 300 ℃ of lower roastings 2 hours, then add 1% graphite and 4% water and mix, be pressed into the tablet of Ф 5 * (4.5-5.5) mm, the Components of Catalysts that makes like this (in oxide) 46% bronze medal with tablet press machine, 37% zinc, 9% magnesium, 6.5% barium, 1.5% cerium.
Embodiment 3: with the 289g copper nitrate, the 401g zinc nitrate, 95.5g magnesium nitrate, 44.7g barium nitrate, 9.5g cerous nitrate is dissolved in the 1L water, be heated to 50 ℃, 500g sodium carbonate is dissolved in the 3L water, and be heated to 70 ℃, then sodium carbonate liquor is slowly dropped in the mixed solution of nitrate, the while rapid stirring is until pH=7.5. is warmed up to 80 ℃ of lower stirrings 1 hour, follow filtration washing, solid material was 120 ℃ of lower oven dry 6 hours, and 300 ℃ of lower roastings 2 hours, the water that then adds graphite and 2% mixed, be pressed into the tablet of Ф 5 * (4.5-5.5) mm, the Components of Catalysts that makes like this (in oxide) 38% bronze medal with tablet press machine, 44% zinc, 6% magnesium, 10.5% barium, 1.5% cerium.
The Performance Ratio of embodiment catalyst and comparative example catalyst is:
Evaluation method: laboratory installation is simulated industrial large production equipment fully, and reactor is Ф 32 stainless steel tubes, and long 2m fills original catalyst particle size 200ml at every turn.
Reaction condition: the pressure normal pressure, 200 ℃ of inlet temperatures, methyl alcohol aniline is than (mole) 1.5, liquid air speed 0.6h
-1Begin to survey in different time period samplings the content of methyl alcohol, aniline, methylphenylamine and DMA from separator from charging.
Comparative test result (one)
Comparative test result (two)
Can find out from above contrast table:
Comparative example in use side reaction is many, and the content of DMA is higher, and the content of the DMA of embodiment is low, illustrates that embodiment's selectively obviously is better than comparative example.
The content of the product methylphenylamine of comparative example is generally at 87-90%, and the content of the product methylphenylamine of embodiment illustrates that generally at 90-93% the conversion ratio of embodiment is higher than comparative example.
Even embodiment 2 and embodiment 3, the principal product content of reaction, and less accessory substance all are better than two comparative examples significantly.This mainly is that the impurity of generation is few because the catalyst selectivity of embodiment is good, and conversion ratio is high.
Therefore can illustrate that the catalyst of the embodiment of the invention is embodiment 1 especially, effect is best.
Claims (4)
1. a novel Chrome-free vapor phase method synthesizes the methylphenylamine catalyst, be used for aniline and methanol vapor phase method fixed bed reaction and produce methylphenylamine, it is characterized in that not containing in the catalyst chromium, in the copper that contains weight 30% ~ 70% in the oxide catalyst, 10% ~ 50% zinc, 5% ~ 20% alkaline-earth metal, 0.2% ~ 2% rare-earth element cerium or lanthanum.
2. catalyst as claimed in claim 1 is characterized in that in the copper that contains weight 30% ~ 60% in the oxide catalyst, 15% ~ 45% zinc, 5% ~ 18% alkaline-earth metal, 0.5% ~ 2% rare-earth element cerium or lanthanum.
3. catalyst as claimed in claim 1 or 2 is characterized in that described alkaline-earth metal is one or both in calcium, magnesium, the barium.
4. catalyst as claimed in claim 1 is characterized in that in the copper that contains weight 30% ~ 50% in the oxide catalyst, 15% ~ 45% zinc, 5% ~ 15% magnesium and barium, 0.5% ~ 1.8% rare-earth element cerium or lanthanum.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113976128A (en) * | 2021-11-29 | 2022-01-28 | 常州大学 | Copper-zinc catalyst for preparing N-methylaniline and N, N-dimethylaniline, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1134313A (en) * | 1995-12-16 | 1996-10-30 | 吉林大学 | Compound oxide catalyst for synthesizing benzene diphenol by phenol-hydrogen peroxide hydroxylation |
| CN1864855A (en) * | 2005-05-20 | 2006-11-22 | 中国科学院大连化学物理研究所 | Transition metal catalyst for gas phase synthesis of N-alkylaniline by aniline and alcohol |
| US20140024522A1 (en) * | 2009-11-10 | 2014-01-23 | Korea Institute Of Energy Research | Catalysts having metal nano-particle catalyst supported on surface-treated natural cellulose fibers and preparation method thereof |
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2013
- 2013-01-07 CN CN201310004072.9A patent/CN103028411B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1134313A (en) * | 1995-12-16 | 1996-10-30 | 吉林大学 | Compound oxide catalyst for synthesizing benzene diphenol by phenol-hydrogen peroxide hydroxylation |
| CN1864855A (en) * | 2005-05-20 | 2006-11-22 | 中国科学院大连化学物理研究所 | Transition metal catalyst for gas phase synthesis of N-alkylaniline by aniline and alcohol |
| US20140024522A1 (en) * | 2009-11-10 | 2014-01-23 | Korea Institute Of Energy Research | Catalysts having metal nano-particle catalyst supported on surface-treated natural cellulose fibers and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 张荣成等: "邻(对)硝基甲苯加氢还原催化剂的制备催化性能", 《工业催化》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113976128A (en) * | 2021-11-29 | 2022-01-28 | 常州大学 | Copper-zinc catalyst for preparing N-methylaniline and N, N-dimethylaniline, preparation method and application thereof |
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