CN102898312A - Method for preparing sec-butylamine through methyl ethyl ketone catalytic ammonization hydrogenation - Google Patents
Method for preparing sec-butylamine through methyl ethyl ketone catalytic ammonization hydrogenation Download PDFInfo
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- CN102898312A CN102898312A CN2011102131598A CN201110213159A CN102898312A CN 102898312 A CN102898312 A CN 102898312A CN 2011102131598 A CN2011102131598 A CN 2011102131598A CN 201110213159 A CN201110213159 A CN 201110213159A CN 102898312 A CN102898312 A CN 102898312A
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- methylethylketone
- butylamine
- sec
- methyl ethyl
- ethyl ketone
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Abstract
The invention relates to a method for preparing sec-butylamine through methyl ethyl ketone catalytic ammonization hydrogenation. According to the invention, a tubular reactor is adopted; methyl ethyl ketone is adopted as a raw material; under the existence of a catalyst containing Ni and Cu or Cr or Zn or Fe, and under the condition that a methyl ethyl ketone volume space velocity is 0.3-2.5h<-1>, methyl ethyl ketone, hydrogen gas and ammonia gas are simultaneously delivered from the upper end of the reactor according to a molar ratio of 1:1-10:1-10; and a methyl ethyl ketone continuous ammonization hydrogenation reaction is carried out under a temperature of 80-160 DEG C and a normal pressure, such that sec-butylamine can be obtained by continuous preparation. According to the invention, a preparation process of the catalyst is simple, a metal load is low, and a catalytic activity is high; the reaction conditions are mild, and high-yield sec-butylamine can be obtained under normal pressure; and only trace sec-butanol and di-sec-butylamine by-products are produced. The volume space velocity of methyl ethyl ketone is high, the process is simple, and continuous production can be carried out, such that production cost is reduced, and the method is suitable for industrialization and popularization. A conversion rate of methyl ethyl ketone can reach 90-100%, and sec-butylamine selectivity is higher than 90%.
Description
Technical field
The present invention relates to the method for the standby sec-butylamine of a kind of methylethylketone catalytic ammoniation Hydrogenation.
Background technology
Sec-butylamine is a kind of important organic chemical industry's intermediate, is widely used in the industries such as medicine, agricultural chemicals, dyestuff, auxiliary chemicals, rubber.Sec-butylamine has the effect of anti-mildew fresh-keeping, and as far back as 1975, it was low toxicity that United Nations's health organization and grain tissue are recommended sec-butylamine, without teratogenesis, without the good preservation agent of carcinogenesis.The synthetic method of sec-butylamine mainly contains at present: sec-butyl alcohol amination and hydrogenation, Diacetylmonoxime reduction method, methylethylketone amination and hydrogenation and butylene amination and hydrogenation.
1, sec-butyl alcohol amination and hydrogenation method: Chai Huanlong (agricultural chemicals, 1983,06:33-42) take sec-butyl alcohol as raw material continuous production sec-butylamine, Ni-Cr-HPO
3Be catalyzer, at 170～190 ℃, the optimum mol ratio is sec-butyl alcohol: hydrogen: ammonia=1:3:5(mol ratio), and liquid air speed 0.1～0.2h
-1, the transformation efficiency of sec-butyl alcohol is up to 98%, and the selectivity of sec-butylamine only has 92%, its reaction.Patent report (application number 200510061485.6) is also arranged take sec-butyl alcohol as raw material, take the modified cobalt that contains Al, Ba as catalyzer, at 110～180 ℃, sec-butyl alcohol: hydrogen: ammonia=1:1～5:2～6, liquid air speed 0.2～0.6h
-1, reaction pressure 1.0～2.0MPa, the transformation efficiency of sec-butyl alcohol reaches 100%, and the highest yield of sec-butylamine is 98.5%.But this class methods temperature of reaction is high, and pressure is high, and the liquid air speed is too low, and the industrialization cost is higher, is unsuitable for suitability for industrialized production.
2, Diacetylmonoxime reduction method: document is arranged, and (CanadianJournalofChemistry, 1981,59 (20): 3007-11) report adopts the lithium aluminium hydride reduction Diacetylmonoxime to obtain target product.Also have document (the Hunan chemical industry, 1992,02:36-37) adopt sodium Metal 99.5 and ethanol to make reductive agent, the yield of sec-butylamine is 81%.Having patent ZL200610052532.5 to adopt Raney's nickel is catalyzer Study on Catalytic Amination of Alcohols Diacetylmonoxime in solvent, 1.0～6.0MPa in autoclave, and 20～150 ℃, the highest yield of sec-butylamine is 93.1%.The used catalyzer cost of above method is high, and whole reaction process step is more, and therefore operational difficulty causes production cost too high.
3, butylene amination hydrogenation method: having patent (USP3,412,158) report to adopt butene-1 and butene-2 is raw material, makees catalyzer with basic metal, and under the hyperpressure of 98MPa, yield also only is 29.4%.This method hypertonia, yield is low, can't realize industrialization.
4, methylethylketone amination and hydrogenation method is immediate prior art, adopt Ni catalyzer doped with Cu, Mg, Ba in the Chinese patent ZL200410011610.8 autoclave, 170～200 ℃, the mol ratio of methylethylketone and ammonia, hydrogen is 1:1.2:1.2, the transformation efficiency of methylethylketone is 30～42%, and selectivity is 70～97%.In addition, have bibliographical information (Fusun PetroleumCollege's journal, 2003,23(1): 1-3), in autoclave take methylethylketone as raw material synthetic sec-butylamine, catalyzer is the modification Raney's nickel, 140 ℃, 6.0MPa, the yield 91.5% of sec-butylamine.Above-mentioned the deficiencies in the prior art are: still reaction temperature high pressure is high, operational difficulty.In addition, also have document (agricultural chemicals, 1983,06:33-42) report tubular type continuous production sec-butylamine is with Ni-Cr-HPO
3Be catalyzer, at 110～130 ℃, methylethylketone: hydrogen: ammonia=1:3.5:4.5(mol ratio), liquid air speed 0.1～0.2h
-1, the transformation efficiency of methylethylketone is 99%, the selectivity of sec-butylamine is 93.3%.In this tubular type successive reaction, the liquid air speed is too low, is unfavorable for suitability for industrialized production.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of technique, and yield is high, the method for the methylethylketone continuous production sec-butylamine that can react under mild conditions.
The present invention is for achieving the above object, and is to realize by such technical scheme: adopting tubular reactor, take methylethylketone as raw material, in the presence of the catalyzer that contains Ni and Cu or Cr or Zn or Fe, is 0.3～2.5h at the volume space velocity of methylethylketone
-1Condition under, with methylethylketone, hydrogen and ammonia take mol ratio as 1:1～10:1～10, pass into from the reactor upper end continuously simultaneously, temperature remains on 80～160 ℃, carry out the continuous amination and hydrogenation reaction of methylethylketone under the normal pressure, but continuous production obtains sec-butylamine, the collecting reaction product continuously from the lower end of reactor, and isolated ammonia and hydrogen return recycling.Under these conditions, the transformation efficiency of methylethylketone can reach 90～100%, and the selectivity of sec-butylamine is greater than 90%.
Further research finds that other conditions are constant, when the volume space velocity of methylethylketone is 0.4～2.0h
-1, the temperature mol ratio that remains on 90～150 ℃, methylethylketone, hydrogen and ammonia is under the condition of 1:1～8:1～8, the transformation efficiency of methylethylketone has further lifting, can reach 95～100%, the selectivity of sec-butylamine is greater than 93%.
Optimum reaction conditions is that the volume space velocity of methylethylketone is 0.5～1.5h
-1, the temperature mol ratio that remains on 100～130 ℃, methylethylketone, hydrogen and ammonia is 1:2～6:2～5, so, the transformation efficiency of methylethylketone is the highest, can reach 99～100%, the selectivity of sec-butylamine can reach more than 97%.
In above-mentioned each reaction, need be reduced activation in 300～600 ℃ of hydrogen streams before catalyzer uses, each metallic element that exists with the form that guarantees in the catalyzer with oxide compound is reduced into corresponding metallographic phase.
The preparation of above-mentioned catalyzer can adopt the impregnated with nitrate of Ni and Cu or Cr or Zn or Fe on carrier, and steaming desolventizes, 120 ℃ of dryings 10～20 hours, and 300～800 ℃ of roastings 4～10 hours, 300～600 ℃ of reduction made catalyzer in 6～12 hours in the hydrogen stream.Wherein the Ni element is 1～20% with respect to the weight percentage of carrier, and all the other metallic elements are 1～5% with respect to the weight percentage of carrier.Carrier is γ-Al
2O
3, TiO
2, Al
2O
3-TiO
2In at least a.
In above-mentioned reaction, best catalyzer is Ni-Zn, and its best preparation method is the same, wherein the Ni element with respect to the weight percentage of carrier be 1～10%, Zn with respect to the weight percentage 5% of carrier, carrier is γ-Al
2O
3, TiO
2, Al
2O
3-TiO
2In at least a, the catalyst activity that obtains with this is optimum.
The present invention has the following advantages:
1. the preparation technology of catalyzer is simple, and content of metal is low, and catalytic activity is high.
2. reaction conditions is gentle, can obtain the sec-butylamine of high yield under normal pressure; Sec-butyl alcohol and di-sec-butylamine by product that trace is only arranged.
3. the volume space velocity of methylethylketone is high, and technique is simple, can produce continuously, has reduced production cost, is suitable for industrial application.
Embodiment
Embodiment 1
The tubular fixed-bed Study on Catalytic Amination of Alcohols hydrogenator of long 400mm and internal diameter 12mm is adopted in test.
The preparation of catalyzer: with 50g carrier γ-Al
2O
3Ball (Φ 2-3mm) impregnated in the nitrate aqueous solution of Ni and Zn, and steaming desolventizes, 120 ℃ of dryings 12 hours, and 500 ℃ of roastings make 10%Ni/5%Zn/ γ-Al after 10 hours
2O
3Catalyzer activates 8 hours at 500 ℃ of logical hydrogen reducings before the reaction.
Raw material methylethylketone, hydrogen and ammonia are inputted continuously from the upper end import of tubular reactor, after the amination and hydrogenation reaction, collect the 1 hour sampling analysis in interval after the on-line analysis of reaction product process gas-chromatography.
Reaction conditions: methylethylketone, hydrogen and ammonia are take mol ratio as 1:6:5, and the volume space velocity of methylethylketone is 1.5h
-1, normal pressure, 100 ℃ of reactions, but continuous production obtains sec-butylamine, and the transformation efficiency of methylethylketone is 85%, and the selectivity of sec-butylamine is 90%.
Embodiment 2
Adopt the catalyzer of embodiment 1, reaction conditions: methylethylketone, hydrogen and ammonia are take mol ratio as 1:5:2, and the volume space velocity of methylethylketone is 1.0h
-1, normal pressure, 130 ℃ of reactions, but continuous production obtains sec-butylamine, and the transformation efficiency of methylethylketone can reach 100%, and the selectivity of sec-butylamine is greater than 95%.
Embodiment 3-7
Adopt embodiment 1 the method preparation 15%Ni/5%Zn/ γ-Al
2O
3Catalyzer, methylethylketone, hydrogen and ammonia are take mol ratio as 1:3:2, and the volume space velocity of methylethylketone is respectively 0.3h
-1, 0.4h
-1, 0.5h
-1, 1.0h
-1, 1.5h
-1, 2.0h
-1, normal pressure, 130 ℃ of reactions, but continuous production obtains sec-butylamine, and reaction result sees Table 1.
Table 1
| ? | Methylethylketone air speed/h -1 | The methylethylketone transformation efficiency | The selectivity of sec-butylamine |
| Embodiment 3 | 0.3 | 100 | 98.4 |
| Embodiment 4 | 0.4 | 100 | 98.6 |
| Embodiment 5 | 0.5 | 100 | 99 |
| Embodiment 6 | 1.0 | 100 | 97.3-98.8 |
| Embodiment 7 | 1.5 | 99-100 | 94.6-96.1 |
| Embodiment 8 | 2.0 | 96.2-98 | 93-94.8 |
Embodiment 9
Make in the catalyzer 15%Ni/5%Cu/Al-Ti(carrier according to the method for embodiment 1 and to contain 20%Ti).Methylethylketone, hydrogen and ammonia are take mol ratio as 1:3:2, and the volume space velocity of methylethylketone is 1.5h
-1, normal pressure, 120 ℃ of reactions, but continuous production obtains sec-butylamine, and the transformation efficiency of methylethylketone is 95%, and the selectivity of sec-butylamine is 85%, and Main By product is sec-butyl alcohol.
Embodiment 10
Make in the catalyzer 15%Ni/5%Cr/Al-Ti(carrier according to the method for embodiment 1 and to contain 20%Ti).Methylethylketone, hydrogen and ammonia are take mol ratio as 1:2:2.5, and the volume space velocity of methylethylketone is 1.0h
-1, normal pressure, 130 ℃ of reactions, but continuous production obtains sec-butylamine, and the transformation efficiency of methylethylketone is 88%, and the selectivity of sec-butylamine is 83%.
Embodiment 11
Adopt the catalyzer of embodiment 9, methylethylketone, hydrogen and ammonia are take mol ratio as 1:5:2, and the volume space velocity of methylethylketone is 0.8h
-1, normal pressure, 100 ℃ of reactions, but continuous production obtains sec-butylamine, and the transformation efficiency of methylethylketone is 80%, and the selectivity of sec-butylamine reaches 90%.
Embodiment 12
Make the 10%Ni/5%Fe/Al-Ti catalyzer according to embodiment 1, methylethylketone, hydrogen and ammonia are take mol ratio as 1:5:3, and the volume space velocity of methylethylketone is 2.0h
-1, normal pressure, 80 ℃ of reactions, but continuous production obtains sec-butylamine, and the transformation efficiency of methylethylketone is 60%, and the selectivity of sec-butylamine reaches 76%.
Claims (6)
1. the method for a methylethylketone continuous production sec-butylamine is characterized in that: adopting tubular reactor, take methylethylketone as raw material, in the presence of the catalyzer that contains Ni and Cu or Cr or Zn or Fe, is 0.3～2.5h at the volume space velocity of methylethylketone
-1Condition under, with methylethylketone, hydrogen and ammonia take mol ratio as 1:1～10:1～10, pass into from the reactor upper end continuously simultaneously, temperature remains on 80～160 ℃, carry out the continuous amination and hydrogenation reaction of methylethylketone under the normal pressure, but continuous production obtains sec-butylamine, the collecting reaction product continuously from the lower end of reactor, and isolated ammonia and hydrogen return recycling.
2. the method for methylethylketone continuous production sec-butylamine according to claim 1, it is characterized in that: the volume space velocity of described methylethylketone is 0.4～2.0h
-1, the temperature mol ratio that remains on 90～150 ℃, methylethylketone, hydrogen and ammonia is 1:1～8:1～8.
3. the method for methylethylketone continuous production sec-butylamine according to claim 1, it is characterized in that: the volume space velocity of described methylethylketone is 0.5～1.5h
-1, the temperature mol ratio that remains on 100～130 ℃, methylethylketone, hydrogen and ammonia is 1:2～6:2～5.
4. the method for arbitrary described methylethylketone continuous production sec-butylamine according to claim 1-3, it is characterized in that: in 300～600 ℃ of hydrogen streams, be reduced activation before urging describedization agent to use, be reduced into corresponding metallographic phase with each metallic element that exists with the form of oxide compound in the assurance catalyzer.
5. according to claim 4 the method for methylethylketone continuous production sec-butylamine, it is characterized in that: described catalyzer adopts the impregnated with nitrate of Ni and Cu or Cr or Zn or Fe on carrier, steaming desolventizes, 120 ℃ of dryings 10～20 hours, 300～800 ℃ of roastings 4～10 hours, 300～600 ℃ of reduction made in 6～12 hours in the hydrogen stream, and wherein the Ni element is 1～20% with respect to the weight percentage of carrier, all the other metallic elements are 1～5% with respect to the weight percentage of carrier, and carrier is γ-Al
2O
3, TiO
2, Al
2O
3-TiO
2In at least a.
6. according to claim 4 the method for methylethylketone continuous production sec-butylamine, it is characterized in that: described catalyzer is Ni-Zn, wherein the Ni element with respect to the weight percentage of carrier be 1～10%, Zn with respect to the weight percentage 5% of carrier, carrier is γ-Al
2O
3, TiO
2, Al
2O
3-TiO
2In at least a.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262165A (en) * | 2014-09-10 | 2015-01-07 | 浙江建业化工股份有限公司 | Preparation method of n-butylamine |
| CN111659404A (en) * | 2020-06-30 | 2020-09-15 | 天津大学 | Supported core-shell structure ZnO catalyst and preparation method and application thereof |
| CN114436826A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing sec-butylamine through post-etherification C4 by supergravity method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1795986A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院兰州化学物理研究所 | Catalyst for preparing sec-butylamine through catalyzing, aminating and hydrogenizing butanone, and preparaation method |
| US20070232833A1 (en) * | 2004-05-13 | 2007-10-04 | Basf Aktiengesellschaft | Method for the Continuous Production of an Amine |
| CN101648875A (en) * | 2009-09-21 | 2010-02-17 | 浙江新化化工股份有限公司 | Method for continuously preparing di-sec-butylamine |
| CN101671255A (en) * | 2009-08-10 | 2010-03-17 | 乐斯化学有限公司 | Method for producing 3-amylamine |
-
2011
- 2011-07-28 CN CN2011102131598A patent/CN102898312A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070232833A1 (en) * | 2004-05-13 | 2007-10-04 | Basf Aktiengesellschaft | Method for the Continuous Production of an Amine |
| CN1795986A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院兰州化学物理研究所 | Catalyst for preparing sec-butylamine through catalyzing, aminating and hydrogenizing butanone, and preparaation method |
| CN101671255A (en) * | 2009-08-10 | 2010-03-17 | 乐斯化学有限公司 | Method for producing 3-amylamine |
| CN101648875A (en) * | 2009-09-21 | 2010-02-17 | 浙江新化化工股份有限公司 | Method for continuously preparing di-sec-butylamine |
Non-Patent Citations (3)
| Title |
|---|
| 柴焕龙: "新型杀菌剂仲丁胺的合成研究", 《南昌大学学报(工科版)》 * |
| 柴焕龙: "杀菌剂仲丁胺的合成研究", 《南昌大学学报(工科版)》 * |
| 王晓立等: "甲乙酮催化氨化加氢合成仲丁胺工艺研究", 《抚顺石油学院学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262165A (en) * | 2014-09-10 | 2015-01-07 | 浙江建业化工股份有限公司 | Preparation method of n-butylamine |
| CN104262165B (en) * | 2014-09-10 | 2016-08-24 | 浙江建业化工股份有限公司 | The preparation method of n-butylamine |
| CN111659404A (en) * | 2020-06-30 | 2020-09-15 | 天津大学 | Supported core-shell structure ZnO catalyst and preparation method and application thereof |
| WO2022000923A1 (en) * | 2020-06-30 | 2022-01-06 | 天津大学 | Supported core-shell structure zno catalyst, preparation method therefor and application thereof |
| GB2605010A (en) * | 2020-06-30 | 2022-09-21 | Univ Tianjin | Supported core-shell structure ZnO catalyst, preparation method therefor and application thereof |
| GB2605010B (en) * | 2020-06-30 | 2024-05-15 | Univ Tianjin | Supported core-shell structure ZnO catalyst, preparation method and use thereof |
| CN114436826A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing sec-butylamine through post-etherification C4 by supergravity method |
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