CN103028411B - 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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- CN103028411B CN103028411B CN201310004072.9A CN201310004072A CN103028411B CN 103028411 B CN103028411 B CN 103028411B CN 201310004072 A CN201310004072 A CN 201310004072A CN 103028411 B CN103028411 B CN 103028411B
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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.In catalyst, not containing chromium, both reduce the pollution of chromium in Catalyst Production, reduced again the pollution of chromium in catalyst use procedure and downstream product; During with this Catalyst Production methylphenylamine, cross the N that reaction forms, N mono-dimethyl benzene amine content is extremely low.
Background technology
Utilizing calandria type fixed bed reactor vapor phase method to produce methylphenylamine is a kind of ripe advanced technique, the history of domestic existing nearly 30 years, the catalyst using on domestic industry device is at present copper, zinc, the cylindrical compressing tablet catalyst of chromium, and stable performance is used model widely to have CNW-1 and QC-5 etc.
Chromium element in 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 have the problem of pollution of chromium.
Summary of the invention
The object 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: the synthetic methylphenylamine catalyst of novel Chrome-free vapor phase method, produce methylphenylamine for aniline and methanol vapor phase method fixed bed reaction, it is characterized in that not containing chromium in catalyst, catalyst is containing 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, barium.
The preferred scheme of catalyst of the present invention: catalyst is containing 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 is containing the copper of weight (in oxide) 30% ~ 50%, 15% ~ 45% zinc, 5% ~ 15% magnesium and barium, 0.5% ~ 1.8% rare-earth element cerium or lanthanum.
Usually, catalyst of the present invention adopts coprecipitation preparation, concrete technology flow process is: by a certain proportion of copper nitrate, zinc nitrate, magnesium nitrate, barium nitrate and cerous nitrate or lanthanum nitrate water dissolve to obtain nitrate mixed solution, with hot water preparation sodium carbonate liquor or sodium bicarbonate aqueous solution, then nitrate solution is added to (or in sodium bicarbonate solution) in sodium carbonate liquor, also can be by sodium carbonate liquor (or sodium bicarbonate solution), add nitrate mixed solution, react to terminal after pH=6.0-8.5, filter material, wash away the sodium ion in material, then dry, and roasting at 320-450 ℃, add afterwards suitable quantity of water and graphite, with rotary tablet machine compacting Ф 5 × (4.5-5.5) tablet of mm.Catalyst needs before using in nitrogen, to prepare certain density hydrogen through the step of reduction, heats up stage by stage, does not go out reductive water until do not consume hydrogen.
Catalyst of the present invention is not containing chromium, and catalyst performance reaches and exceedes the properties of product that current commercial plant uses, and intensity is high, conversion ratio and selectively high.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 in comparative example and embodiment is nitrate trihydrate copper and zinc nitrate hexahydrate and six water cerous nitrates below, and magnesium nitrate hexahydrate and barium nitrate.
Comparative example 1:
The catalyst for aniline and methanol vapor phase method fixed bed reaction production methylphenylamine of industrial application at present, main component is copper, zinc, chromium.Be of a size of Ф 5 × (4.5-5.5) mm.
Comparative example 2: the catalyst for aniline and methanol vapor phase method fixed bed reaction production methylphenylamine that applicant produced in the past.
By the Gerhardite of 256.7 kilograms, the zinc nitrate hexahydrate of 178.5 kilograms, the Chromium nitrate (Cr(NO3)3),nonahydrate of 72.8 kilograms is poured allotment bucket into, then adds water and make the mixed liquor A of 1.5 cubic metres; The another natrium carbonicum calcinatum that adds 180 kilograms in settling box, is dissolved in water and is made into the alkali lye B of 3 cubic metres and is heated to 70 degree; Then mixed liquor A is slowly splashed in alkali lye B, until add.Then filtration washing, and dry under 100 degree, and the material obtaining adds graphite moulding, the finished catalyst of system.This catalyst (in oxide) copper 40.3%, zinc 23.2%, containing chromium 7.3%.
Embodiment 1: by 365g copper nitrate, 392g zinc nitrate, 47.8g magnesium nitrate, the cerous nitrate of 21.3g barium nitrate and 6.3g is dissolved in 1L water, be heated to 50 ℃, 650g sodium acid carbonate is dissolved in 3L water, and be heated to 70 ℃, then sodium bicarbonate solution is slowly dropped in the mixed solution of nitrate, rapid stirring simultaneously, until being warmed up to 80 ℃, stirs again 1 hour pH=7.5., then filtration washing, solid material is dried 6 hours at 120 ℃, roasting 2 hours at 300 ℃, then add 2% graphite and 4% water to mix, be pressed into Ф 5 × (4.5-5.5) tablet of mm with tablet press machine, Components of Catalysts (in oxide) 48% bronze medal making like this, 43% zinc, 3% magnesium, 5% barium, 1.% cerium.
Embodiment 2:
By 350g copper nitrate, 338g zinc nitrate, 143g magnesium nitrate, 27.7g barium nitrate and 9.5g cerous nitrate are dissolved in 1L water, be heated to 50 ℃, 500g sodium carbonate is dissolved in 3L water, and be heated to 70 ℃, then sodium carbonate is slowly dropped in the mixed solution of nitrate, rapid stirring simultaneously, until being warmed up to 80 ℃, stirs again 1 hour pH=7.5., then filtration washing, solid material is dried 6 hours at 120 ℃, roasting 2 hours at 300 ℃, then add 1% graphite and 4% water to mix, be pressed into Ф 5 × (4.5-5.5) tablet of mm with tablet press machine, Components of Catalysts (in oxide) 46% bronze medal making like this, 37% zinc, 9% magnesium, 6.5% barium, 1.5% cerium.
Embodiment 3: by 289g copper nitrate, 401g zinc nitrate, 95.5g magnesium nitrate, 44.7g barium nitrate, 9.5g cerous nitrate is dissolved in 1L water, be heated to 50 ℃, 500g sodium carbonate is dissolved in 3L water, and be heated to 70 ℃, then sodium carbonate liquor is slowly dropped in the mixed solution of nitrate, rapid stirring simultaneously, until being warmed up at 80 ℃, stirs 1 hour pH=7.5., then filtration washing, solid material is dried 6 hours at 120 ℃, roasting 2 hours at 300 ℃, then add the water of graphite and 2% to mix, be pressed into Ф 5 × (4.5-5.5) tablet of mm with tablet press machine, Components of Catalysts (in oxide) 38% bronze medal making like this, 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 completely, reactor is Ф 32 stainless steel tubes, long 2m fills original catalyst particle size 200ml at every turn.
Reaction condition: pressure normal pressure, 200 ℃ of inlet temperatures, methyl alcohol aniline than (mole) 1.5, liquid air speed 0.6h
-1start 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 is selectively obviously 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 is generally at 90-93%, illustrates that 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, be all better than two comparative examples significantly.This is mainly that the impurity of generation is few because the catalyst selectivity of embodiment is good, and conversion ratio is high.
Therefore can illustrate, the catalyst of the embodiment of the present invention is embodiment 1 especially, and effect is best.
Claims (4)
1. the synthetic methylphenylamine catalyst of Chrome-free vapor phase method, produce methylphenylamine for aniline and methanol vapor phase method fixed bed reaction, it is characterized in that in catalyst not containing chromium, in the copper containing weight 30% ~ 70%, 10% ~ 50% zinc, 5% ~ 20% alkaline-earth metal, 0.2% ~ 2% rare-earth element cerium or lanthanum in oxide catalyst, described catalyst adopts coprecipitation preparation: by the copper nitrate of aforementioned proportion, zinc nitrate, magnesium nitrate, barium nitrate and cerous nitrate or lanthanum nitrate water dissolve to obtain nitrate mixed solution, with hot water preparation sodium carbonate liquor or sodium bicarbonate aqueous solution, then nitrate solution is added in sodium carbonate liquor or in sodium bicarbonate solution, or by sodium carbonate liquor or sodium bicarbonate solution, add nitrate mixed solution, react to terminal after pH=6.0-8.5, filter material, wash away the sodium ion in material, then dry, and roasting at 320-450 ℃, add afterwards suitable quantity of water and graphite, with rotary tablet machine compacting Ф 5 × (4.5-5.5) tablet of mm.
2. catalyst as claimed in claim 1, is characterized in that in the copper containing weight 30% ~ 60%, 15% ~ 45% zinc, 5% ~ 18% alkaline-earth metal, 0.5% ~ 2% rare-earth element cerium or lanthanum in oxide catalyst.
3. catalyst as claimed in claim 1 or 2, is characterized in that described alkaline-earth metal is one or both in calcium, magnesium, barium.
4. catalyst as claimed in claim 1, it is characterized in that in oxide catalyst containing the copper of weight 30% ~ 50%, 15% ~ 45% zinc, 5% ~ 15% magnesium and barium, 0.5% ~ 1.8% rare-earth element cerium or lanthanum.
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| CN100408179C (en) * | 2005-05-20 | 2008-08-06 | 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 |
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Address after: Xinhuang town of Liuhe District of Nanjing City, Jiangsu province 211516 Patentee after: Nanjing John Lone new Mstar Technology Ltd Address before: Xinhuang town of Liuhe District of Nanjing City, Jiangsu province 211516 Patentee before: Nanjing Zunlong Chemical Co., Ltd. |