CN102690204B - Method for preparing cyclohexanediamine - Google Patents
Method for preparing cyclohexanediamine Download PDFInfo
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- CN102690204B CN102690204B CN201110072096.9A CN201110072096A CN102690204B CN 102690204 B CN102690204 B CN 102690204B CN 201110072096 A CN201110072096 A CN 201110072096A CN 102690204 B CN102690204 B CN 102690204B
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- cyclohexanediamine
- phenylenediamine
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- ammonia
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Abstract
The invention discloses a method for preparing cyclohexanediamine. The method is characterized in that a reaction system comprises ammonia, hydrogen, a catalyst and o-phenylenediamine or m-phenylenediamine or p-phenylenediamine; a reaction temperature is in a range of 120 to 220 DEG C; reaction pressure is in a range of 1.0 to 20.0MPa; a weight ratio of o-phenylenediamine or m-phenylenediamine or p-phenylenediamine to isopropanol(tetrahydrofuran) to the catalyst to NaNO2 to water to liquid ammonia is (8-30): (30-70): (1-8): (0.1-1.2): (1-10): (0.5-5); the catalyst adopts Al2O3, active carbon or SiO2 as a carrier and is loaded with one or more of precious metals of Ru and Pd as active ingredients and preferably, is loaded with Ru; one or more auxiliary agents are selected from Re, Co, Ni, Fe and their oxides; and in a slurry-bed reactor, under the ammonia reaction of the catalyst, the high activity and high selectivity transformation of o-phenylenediamine or m-phenylenediamine or p-phenylenediamine and isopropanol(tetrahydrofuran) respectively into 1,2-, 1,3- and 1,4-cyclohexanediamine is realized.
Description
Technical field
The present invention relates to a kind ofly take phenylenediamine alcohol (tetrahydrofuran (THF)) solution and face the method that ammonia hydrogenation is prepared respectively cyclohexanediamine as raw material, by a kind of, for take O-Phenylene Diamine or mphenylenediamine or Ursol D alcohol (tetrahydrofuran (THF)) solution, as facing ammonia hydrogenation, raw material is separately converted to 1 specifically, 2-cyclohexanediamine or 1, the method of 3-cyclohexanediamine or Isosorbide-5-Nitrae-cyclohexanediamine.
Technical background
Cyclohexanediamine is a kind of solidifying agent of important epoxy resin, and what wherein consumption was the widest is 1,2-cyclohexanediamine, 1,3-cyclohexanediamine and Isosorbide-5-Nitrae-cyclohexanediamine.For colourless transparent liquid and white solidliquid mixture, in weaving, papermaking, the fields such as leatheroid and plastics have a wide range of applications.Can be used as dyestuff, medicine intermediate, the raw materials such as aminomethyl acid esters and polyamide.
Industrial 1,2-cyclohexanediamine, as the byproduct of nylon 66 production processes, is often produced the raw material of O-Phenylene Diamine as dehydrogenation.United States Patent (USP) 5,663,438 have reported Pd-Pt/Al
2o
3phenol on catalyzer, ammonia and hydrogen are the method for waste hexahydroaniline.United States Patent (USP) 3,450,759 and 5,973,207 find that the corresponding methyl cyclohexane diamines of tolylene diamine Hydrogenation is difficulty very, and object efficiency of pcr product is lower, and especially toluylenediamine, only has after toluylenediamine separation, could improve the yield of object product.Due in O-Phenylene Diamine and Ursol D hydrogenation process, be easy to remove an amido on the one hand, become hexahydroaniline, the cyclohexanediamine generating is on the other hand easy to polymerization and generates nitrogenous superpolymer, not only cause catalyst deactivation, reduced the selectivity of object product simultaneously.
United States Patent (USP) 5,072,044 has described 1,2-cyclohexanediamine Oxidative Dehydrogenation faces phenylenediamine, the process of 360-380 ℃ of Oxidative Dehydrogenation aniline on the Pd catalyzer that discovery hexahydroaniline mixes at Li, but follow a large amount of by products.European patent EP-A-22751, EP-A-53819 and EP-A-167996 have described phenol at NH
3/ H
2next step is converted into hexahydroaniline with Pd catalyst action, almost there is no the generation of aromatic amine.Wherein, EP-A-167996 has reported that phenol is at NH
3/ H
2under Pd catalyst action, first when 180-210 ℃ of low temperature, produce hexahydroaniline, then under the high temperature of 220-250 ℃, hexahydroaniline dehydrogenation generates aniline.United States Patent (USP) 5,360,934 disclose the patent that biconjugate aminocarbonyl phenyl methane hydrogenation is produced biconjugate amido cyclohexyl-methane.But above-mentioned technology is low to the selectivity of product cyclohexanediamine.
Summary of the invention
The object of this invention is to provide and a kind ofly take phenylenediamine and hydrogen and facing the method for preparing cyclohexanediamine under ammonia condition as raw material.
For achieving the above object, preparation 1 provided by the invention, 2-cyclohexanediamine, 1, the method of 3-cyclohexanediamine and Isosorbide-5-Nitrae-cyclohexanediamine, by raw material Ursol D or mphenylenediamine or O-Phenylene Diamine, hydrogen prepares respectively 1 facing under ammonia condition, 2-cyclohexanediamine, 1,3-cyclohexanediamine and Isosorbide-5-Nitrae-cyclohexanediamine.
Reaction system of the present invention is comprised of Ursol D or mphenylenediamine or O-Phenylene Diamine, ammonia, hydrogen and catalyzer; Reaction conditions is: temperature of reaction is 100～220 ℃, better temperature of reaction is that 120～200 ℃ of reaction pressures are 1.0～20.0MPa, preferably reaction pressure is 2.0～15.0MPa, O-Phenylene Diamine or mphenylenediamine or Ursol D: Virahol (tetrahydrofuran (THF)): catalyzer: NaNO
2: water: liquefied ammonia (weight)=8～30: 30～70: 1～8: 0.1～1.2: 1～10: 0.5～5, preferably O-Phenylene Diamine or mphenylenediamine or Ursol D: Virahol (tetrahydrofuran (THF)): catalyzer: NaNO
2: water: liquefied ammonia (weight)=10～28: 35～60: 2～6: 0.3～1.0: 2～8: 0.8～4.
Described catalyzer is with gac or Al
2o
3or SiO
2for carrier, load active component is that precious metal Ru and Pd neutralize one or more, preferably Ru; Auxiliary agent is one or more in the metals such as Re, Co, Ni and Fe or oxide compound; The loading of active ingredient is the 0.1-30.0% of catalyst weight, and the loading of auxiliary agent is catalyst weight 0.1～20%.
Described phenylenediamine is Ursol D or mphenylenediamine or O-Phenylene Diamine, and ammonia is liquefied ammonia, and major product is Isosorbide-5-Nitrae-cyclohexanediamine or 1,3-cyclohexanediamine or 1,2-cyclohexanediamine.
Catalyzer of the present invention is comprised of carrier and the active ingredient being supported on carrier.Carrier can be gac or Al
2o
3or SiO
2.Load active component is that precious metal Ru and Pd neutralize one or more, preferably Ru.Auxiliary agent is one or more in the metals such as Re, Co, Ni and Fe or oxide compound.The catalyzer that contains said components can adopt the familiar conventional catalyst preparation method in this area as: the precipitator method, pickling process, hydrothermal synthesis method or aforesaid method are combined with.
The present invention compared with prior art, can significantly reduce reaction pressure and energy consumption, and improving facing phenylenediamine and hydrogen under ammonia condition is the selectivity that raw material is prepared as cyclohexanediamine.
Embodiment
The invention provides and a kind ofly take phenylenediamine and hydrogen as raw material (solvent adopts ethanol, THF or Virahol) is facing the method for preparing cyclohexanediamine under ammonia condition, be about to phenylenediamine and hydrogen and facing the process that is catalytically conveted to cyclohexanediamine under ammonia condition.Reaction system is comprised of phenylenediamine, ammonia, hydrogen and catalyzer.In above-mentioned system, phenylenediamine is separately converted to cyclohexanediamine with hydrogen high reactivity, highly selective after certain temperature contacts certain hour with under ammonia pressure with catalyzer.
The present invention can directly be pumped into liquefied ammonia and phenylenediamine/solvent liquid in autoclave paste state bed reactor, and and H
2reaction after mixing.Add ethanol, one or more in THF and Virahol are dissolved as solvent.
Reaction process of the present invention can adopt paste state bed reactor, also can adopt fixed-bed reactor.Preferred paste state bed reactor wherein.
Catalyzer of the present invention can activate by the hydrogen treat under certain condition before using.By the better condition of hydrogen deactivated catalyst, be: GHSV=2400h
-1, 0.2MPaG, 300 ℃, 5 hours recovery times, the catalyzer after activation is through CO
2after passivation, be transferred in autoclave slurry state bed.
Below by specific embodiment, the present invention will be further described.
Embodiment 1
The catalyzer adopting is 5%Ru-2%Re/ coconut husk charcoal.Carrier adopts commodity coconut husk charcoal, is sieved into 150-200 order, before using, through 3% nitric acid dousing, boils 4 hours, and distilled water is washed till pH=7.0 left and right, dries 6 hours for 120 ℃.By conventional pickling process, catalyst activity component Ru and Re are supported on carrier coconut husk charcoal.3.0 grams of catalyzer activated through hydrogen before reaction, and activation condition is: GHSV=2400h
-1, 0.2MPaG, 300 ℃, 5 hours recovery times.Select paste state bed reactor.Temperature of reaction is 170 ℃, 16 grams of O-Phenylene Diamines, and isopropanol solvent volume is 70ml, 3 grams of catalyzer, 4 grams of distilled water, NaNO
20.5 gram, be filled with 2 grams of liquefied ammonia, being filled with hydrogen is 8.0MPa to reacting total pressure, the reaction times is 10h, sampling analysis.SE-30 capillary chromatographic column, fid detector.Press area normalization.Reaction result is summarised in table 1.
Embodiment 2
Employing mphenylenediamine is raw material, and other condition is identical with embodiment 1.
Embodiment 3
Employing Ursol D is raw material, and other condition is identical with embodiment 1.
Embodiment 4
Employing tetrahydrofuran (THF) is solvent, and other condition is identical with embodiment 1.
Embodiment 5
Adopting temperature of reaction is 150 ℃, and other condition is identical with embodiment 1.
Embodiment 6
Adopting temperature of reaction is 190 ℃, and other condition is identical with embodiment 1.
Embodiment 7
Adopting hydrogen pressure is 6.0, and other condition is identical with embodiment 1.
Embodiment 8
Adopting hydrogen pressure is 10.0, and other condition is identical with embodiment 1.
Embodiment 9
Adopting hydrogen pressure is 12.0, and other condition is identical with embodiment 1.
Embodiment 10
Adopting phenylenediamine/catalyst weight ratio is 16: 2, and other condition is identical with embodiment 1.
Embodiment 11
Adopting phenylenediamine/weight ratio is 16: 6, and other condition is identical with embodiment 1.
Embodiment 12
Adopting phenylenediamine/α-amino isopropyl alcohol weight ratio is 16: 45, and other condition is identical with embodiment 1
Embodiment 13
Adopting phenylenediamine/α-amino isopropyl alcohol weight ratio is 16: 65, and other condition is identical with embodiment 1
Embodiment 14
The granularity that employing takes 4.0 grams of catalyzer is that 20-40 order fills in fixed-bed reactor, by phenylenediamine/liquefied ammonia/Virahol/NaNO
2/ water (mix in advance, ammonia/phenylenediamine weight ratio is 1/8) pumps in preheater and is mixed into reactor with hydrogen, H
2pressure is 8.0MPa, H
2air speed is 1000h
-1, other condition is identical with embodiment 1.
Phenylenediamine of the present invention and hydrogen are that raw material is prepared cyclohexanediamine reaction evaluating result and is summarised in table 1 under facing ammonia condition.
Table 1: face the condition optimizing evaluation result that phenylenediamine and hydrogen under ammonia condition are converted into cyclohexanediamine
* other product mainly comprises a series of products that cyclohexanediamine further reacts with Virahol.
Press the catalyzer of embodiment 1, reaction conditions and raw material form, and have carried out catalyzer and have repeated reuse more than 8 times, do not find that catalyst activity and selectivity has obvious downtrending.
Claims (5)
1. a method of preparing cyclohexanediamine, reaction system is by the isopropanol water solution of O-Phenylene Diamine or mphenylenediamine or Ursol D or tetrahydrofuran aqueous solution, liquefied ammonia, hydrogen, NaNO
2form with catalyzer, primary product is respectively 1,2-cyclohexanediamine, 1,3-cyclohexanediamine and Isosorbide-5-Nitrae-cyclohexanediamine, and reaction conditions is:
Temperature of reaction is 100～220 ℃, and reaction pressure is 1.0～20.0MPa, O-Phenylene Diamine by weight or mphenylenediamine or Ursol D: Virahol or tetrahydrofuran (THF): catalyzer: NaNO
2: water: liquefied ammonia=8～30:30～70:1～8:0.1～1.2:1～10:0.5～5;
Described catalyzer is with gac, Al
2o
3or SiO
2for carrier, load active component is precious metal Ru, and auxiliary agent is Re, and the loading of active ingredient is catalyst weight 5%, and the loading of auxiliary agent is catalyst weight 2%,
Wherein said reaction is carried out facing under ammonia condition in paste state bed reactor.
2. method according to claim 1, wherein, reaction pressure is 2.0～15.0MPa.
3. method according to claim 1, wherein, temperature of reaction is 120～200 ℃.
4. method according to claim 1, wherein, O-Phenylene Diamine by weight or mphenylenediamine or Ursol D: Virahol or tetrahydrofuran (THF): catalyzer: NaNO
2: water: liquefied ammonia=10～28:35～60:2～6:0.3～1.0:2～8:0.5～5.
5. a preparation method who prepares the catalyzer using in cyclohexanediamine method claimed in claim 1, the combination that described catalyzer adopts the precipitator method, pickling process, hydrothermal synthesis method or aforesaid method by active constituent loading on carrier.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2905273B1 (en) * | 2014-02-05 | 2018-06-06 | Covestro Deutschland AG | Process for hydrogenating aromatic di- and polyamines |
| CN104327246B (en) * | 2014-10-16 | 2018-02-13 | 宁波大学 | A kind of chiral diamine polymer and its synthetic method |
| CN105237407B (en) * | 2015-11-04 | 2017-03-29 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of 1,2 cyclohexanediamine |
| CN106582634A (en) * | 2016-11-16 | 2017-04-26 | 盘锦格林凯默科技有限公司 | Highly active ruthenium-carbon catalyst modified by transition metal atoms and preparation method thereof |
| CN106994344B (en) * | 2017-03-31 | 2021-05-25 | 江苏清泉化学股份有限公司 | Method and catalyst for preparing methylcyclohexanediamine by selective hydrogenation of toluenediamine |
| CN111018727A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Method for producing glycine |
| CN109553538B (en) * | 2018-11-28 | 2021-10-22 | 南京红宝丽聚氨酯有限公司 | Continuous preparation method of 1, 2-cyclohexanediamine |
| CN112898164B (en) * | 2019-12-03 | 2022-03-04 | 中国科学院大连化学物理研究所 | Method for preparing 1, 6-hexamethylene diamine from 5-hydroxymethylfurfural |
| CN117358235A (en) * | 2023-08-01 | 2024-01-09 | 江苏清泉化学股份有限公司 | Catalyst for preparing MACM by continuous hydrogenation and preparation method and application thereof |
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