CN102775313A - Method for preparing 1, 4-cyclohexanediamine by adding hydrogen continuously at high pressure - Google Patents
Method for preparing 1, 4-cyclohexanediamine by adding hydrogen continuously at high pressure Download PDFInfo
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- CN102775313A CN102775313A CN2012102647996A CN201210264799A CN102775313A CN 102775313 A CN102775313 A CN 102775313A CN 2012102647996 A CN2012102647996 A CN 2012102647996A CN 201210264799 A CN201210264799 A CN 201210264799A CN 102775313 A CN102775313 A CN 102775313A
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- cyclohexanediamine
- high pressure
- dioxane
- ursol
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Abstract
The invention discloses a method for preparing 1, 4-cyclohexanediamine by adding hydrogen continuously at a high pressure. The method includes dissolving phenylenediamine in a 1, 4-Dioxane solution at a temperature of 100 DEG C, feeding the mixture solution continuously into a fixed bed reactor with a temperature ranging from 160 DEG C to 200 DEG C, and keeping the circulating pressure of the hydrogen to between 4 MPa and 8 MPa simultaneously to obtain the 1, 4-cyclohexanediamine under the action of a Ru/Al2O3catalyst. According to the method, the synthesis technological line is short, and the product conversion rate is more than 99%.
Description
Technical field
The present invention relates to a kind of preparation method of cyclohexanediamine, relate in particular to a kind of high pressure serialization hydrogenation preparing 1, the method for 4-cyclohexanediamine.
Background technology
1, the 4-cyclohexanediamine is as symmetrical configuration and do not have the organic amine of aromatic nucleus, is widely used in the production of weaving, papermaking, leatheroid, plastic working, liquid crystal material; The raw material that also can be used as dyestuff, medicine intermediate; Particularly can be used as the raw material of making novel aminomethyl acid esters, polyamide etc.According to 1, the meliority of 4-cyclohexanediamine structure must can replace 1 aspect many purposes, the application of 4-tetramethylenediamine, Ursol D etc. in the future.
At present, find about 1 the preparing method's of 4-cyclohexanediamine report as yet.
Summary of the invention
The object of the present invention is to provide a kind of high pressure serialization hydrogenation preparing 1, the method for 4-cyclohexanediamine.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of high pressure serialization hydrogenation preparing 1, and the method for 4-cyclohexanediamine may further comprise the steps: under 100 ℃; Phenylenediamine is dissolved in 1, and in the 4-dioxane solvent, mixed solution is sent in the fixed-bed reactor continuously; Temperature of reaction is 160 ~ 200 ℃, and simultaneously, keeping hydrogen recycle pressure is 4-8Mpa; Under catalyst action, obtain title product 1, the 4-cyclohexanediamine, reaction equation is following:
Preferably, described 1, the consumption of 4-dioxane and Ursol D mass ratio are at 1:1-5.
Preferably, described 1, the consumption of 4-dioxane and Ursol D mass ratio are at 1:2.
Preferably, said temperature of reaction is 170 ~ 180 ℃.
Preferably, described hydrogen recycle pressure is 6 ~ 8Mpa.
Preferably, described catalyzer comprises active ingredient and carrier, and active ingredient is a kind of in ruthenium or palladium or the nickel, and carrier is an aluminium sesquioxide.
Preferably, described catalyzer is a ruthenium.
The invention has the advantages that: with the Ursol D raw material, 1, the 4-dioxane is a solvent, noble ruthenium is catalyzer (aluminium sesquioxide is a carrier), serialization hydrogenation preparing 1, the 4-cyclohexanediamine, its transformation efficiency reaches more than 99%.
Embodiment
Embodiment 1
Under 100 ℃, the 54g Ursol D is dissolved in 1 of 108g, in the 4-dioxane, this material is sent into through the product pump serialization Ru/Al is housed
2O
3And be warming up in 170 ℃ the shell and tube continuous reaction device, keeping hydrogen recycle pressure simultaneously is 6-8MPa, after the 2h charging finishes; Sampling GC analyzes, and removes solvent 1, the 4-dioxane; Recording Ursol D content is 0.48%, 1, and 4-cyclohexanediamine content is 98.95%.
Embodiment 2
Under 100 ℃, the 108g Ursol D is dissolved in 1 of 216g, in the 4-dioxane, this material is sent into through the product pump serialization Ru/Al is housed
2O
3And be warming up in 170 ℃ the shell and tube continuous reaction device, keeping hydrogen recycle pressure simultaneously is 6-8MPa, after the 4h charging finishes; Sampling GC analyzes, and removes solvent 1, the 4-dioxane; Recording Ursol D content is 0.36%, 1, and 4-cyclohexanediamine content is 99.15%.
Embodiment 3
Under 100 ℃, the 162g Ursol D is dissolved in 1 of 324g, in the 4-dioxane, this material is sent into through the product pump serialization Ru/Al is housed
2O
3And be warming up in 170 ℃ the shell and tube continuous reaction device, keeping hydrogen recycle pressure simultaneously is 6-8MPa, after the 6h charging finishes; Sampling GC analyzes, and removes solvent 1, the 4-dioxane; Recording Ursol D content is 0.30%, 1, and 4-cyclohexanediamine content is 99.16%.
Embodiment 4
Under 100 ℃, the 216g Ursol D is dissolved in 1 of 432g, in the 4-dioxane, this material is sent into through the product pump serialization Ru/Al is housed
2O
3And be warming up in 170 ℃ the shell and tube continuous reaction device, keeping hydrogen recycle pressure simultaneously is 6-8MPa, after the 8h charging finishes; Sampling GC analyzes, and removes solvent 1, the 4-dioxane; Recording Ursol D content is 0.26%, 1, and 4-cyclohexanediamine content is 99.26%.
Claims (7)
1. high pressure serialization hydrogenation preparing 1, the method for 4-cyclohexanediamine may further comprise the steps: under 100 ℃; Phenylenediamine is dissolved in 1, and in the 4-dioxane solvent, mixed solution is sent in the fixed-bed reactor continuously; Temperature of reaction is 160 ~ 200 ℃, and simultaneously, keeping hydrogen recycle pressure is 4-8Mpa; Under catalyst action, obtain title product 1, the 4-cyclohexanediamine, reaction equation is following:
2. a kind of high pressure serialization hydrogenation preparing 1 according to claim 1, the method for 4-cyclohexanediamine is characterized in that: described 1, the consumption of 4-dioxane and Ursol D mass ratio are at 1:1-5.
3. a kind of high pressure serialization hydrogenation preparing 1 according to claim 2, the method for 4-cyclohexanediamine is characterized in that: described 1, the consumption of 4-dioxane and Ursol D mass ratio are at 1:2.
4. the preparation method of a kind of 1,4 cyclohexanedicarboxylic acid according to claim 1, it is characterized in that: said temperature of reaction is 170 ~ 180 ℃.
5. the preparation method of a kind of 1,4 cyclohexanedicarboxylic acid according to claim 1, it is characterized in that: described hydrogen recycle pressure is 6 ~ 8Mpa.
6. the preparation method of a kind of 1,4 cyclohexanedicarboxylic acid according to claim 1, it is characterized in that: described catalyzer comprises active ingredient and carrier, and active ingredient is a kind of in ruthenium or palladium or the nickel, and carrier is an aluminium sesquioxide.
7. the preparation method of a kind of 1,4 cyclohexanedicarboxylic acid according to claim 6, it is characterized in that: described catalyzer is a ruthenium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102647996A CN102775313A (en) | 2012-07-30 | 2012-07-30 | Method for preparing 1, 4-cyclohexanediamine by adding hydrogen continuously at high pressure |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102647996A CN102775313A (en) | 2012-07-30 | 2012-07-30 | Method for preparing 1, 4-cyclohexanediamine by adding hydrogen continuously at high pressure |
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| CN102775313A true CN102775313A (en) | 2012-11-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2012102647996A Pending CN102775313A (en) | 2012-07-30 | 2012-07-30 | Method for preparing 1, 4-cyclohexanediamine by adding hydrogen continuously at high pressure |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304425A (en) * | 2013-06-18 | 2013-09-18 | 姜堰市科研精细化工有限公司 | Preparation method of 1,4-diamido-cyclohexane |
| CN110090641A (en) * | 2019-05-21 | 2019-08-06 | 常州大学 | A kind of catalyst and preparation method and application adding hydrogen 1,3- hexamethylene dimethylamine for m-xylene diamine |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3657345A (en) * | 1969-10-27 | 1972-04-18 | Du Pont | Isomer enrichment of 1 4-cyclohexanediamine |
| CN1200107A (en) * | 1995-09-12 | 1998-11-25 | 巴斯福股份公司 | Method of hydrogenating aromatic compounds in which at least one amino group is bonded to an aromatic nucleus |
| US6369274B1 (en) * | 1998-11-12 | 2002-04-09 | Lonza Ag | Method for producing cyclohexanediamines |
| JP2008074754A (en) * | 2006-09-20 | 2008-04-03 | Iwatani Industrial Gases Corp | METHOD FOR PRODUCING trans-1,4-DIAMINOCYCLOHEXANE |
| CN102503838A (en) * | 2011-11-07 | 2012-06-20 | 四川大学 | Method for preparing diaminocyclohexane by hydrogenation of aromatic diamine |
-
2012
- 2012-07-30 CN CN2012102647996A patent/CN102775313A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3657345A (en) * | 1969-10-27 | 1972-04-18 | Du Pont | Isomer enrichment of 1 4-cyclohexanediamine |
| CN1200107A (en) * | 1995-09-12 | 1998-11-25 | 巴斯福股份公司 | Method of hydrogenating aromatic compounds in which at least one amino group is bonded to an aromatic nucleus |
| US6369274B1 (en) * | 1998-11-12 | 2002-04-09 | Lonza Ag | Method for producing cyclohexanediamines |
| JP2008074754A (en) * | 2006-09-20 | 2008-04-03 | Iwatani Industrial Gases Corp | METHOD FOR PRODUCING trans-1,4-DIAMINOCYCLOHEXANE |
| CN102503838A (en) * | 2011-11-07 | 2012-06-20 | 四川大学 | Method for preparing diaminocyclohexane by hydrogenation of aromatic diamine |
Non-Patent Citations (3)
| Title |
|---|
| HOON SIK KIM 等: "Ru-catalyzed hydrogenation of aromatic diamines: The effect of alkali metal salts", 《JOURNAL OF MOLECULAR CATALYSIS A:CHEMICAL》 * |
| 刘庆林 等: "PDA加氢合成CHDA的工艺", 《华南理工大学学报（自然科学版）》 * |
| 林雪 等: "对苯二胺加氢制备1,4-环己二胺的工艺研究", 《精细石油化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304425A (en) * | 2013-06-18 | 2013-09-18 | 姜堰市科研精细化工有限公司 | Preparation method of 1,4-diamido-cyclohexane |
| CN110090641A (en) * | 2019-05-21 | 2019-08-06 | 常州大学 | A kind of catalyst and preparation method and application adding hydrogen 1,3- hexamethylene dimethylamine for m-xylene diamine |
| CN110090641B (en) * | 2019-05-21 | 2022-03-25 | 常州大学 | Catalyst for preparing 1, 3-cyclohexyldimethylamine by m-xylylenediamine hydrogenation, preparation method and application |
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Application publication date: 20121114 |