CN103896778A - Method for preparing 1,4-cyclohexanediamine at high pressure - Google Patents
Method for preparing 1,4-cyclohexanediamine at high pressure Download PDFInfo
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- CN103896778A CN103896778A CN201310483516.1A CN201310483516A CN103896778A CN 103896778 A CN103896778 A CN 103896778A CN 201310483516 A CN201310483516 A CN 201310483516A CN 103896778 A CN103896778 A CN 103896778A
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- China
- Prior art keywords
- nitrae
- isosorbide
- cyclohexanediamine
- high pressure
- cyclohexanediol
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 0 C*(C1)(C2)C3C1CC2*3 Chemical compound C*(C1)(C2)C3C1CC2*3 0.000 description 3
- VKONPUDBRVKQLM-UHFFFAOYSA-N OC(CC1)CCC1O Chemical compound OC(CC1)CCC1O VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a method for preparing 1,4-cyclohexanediamine at high pressure. The method comprises the following steps: adding 1,4-cyclohexanediol and liquid ammonia or 25% ammonium hydroxide to a high-pressure reaction kettle; and reacting at 10-15MPa for 12 hours, wherein the reaction temperature is 220-250 DEG C, so as to obtain a target product 1,4-cyclohexanediamine. The preparation method disclosed by the invention is short in technological process, low in production cost, and high in production security, the product conversion rate is more than 95%, and the product yield is about 93%.
Description
Technical field
The present invention relates to a kind of preparation method of cyclohexanediamine, relate in particular to a kind of method that high pressure is prepared Isosorbide-5-Nitrae-cyclohexanediamine.
Background technology
1,4-cyclohexanediamine is as symmetrical configuration and without the organic amine of aromatic nucleus, be widely used in the production of weaving, papermaking, leatheroid, plastic working, liquid crystal material, also can be used as the raw material of dyestuff, medicine intermediate, particularly the raw material of novel manufacture aminomethyl acid esters, polyamide etc.Due to the superiority of its structure, must aspect many purposes, replace Putriscine, Ursol D etc. in the future.
Be widely used at present Ursol D shortening and prepare Isosorbide-5-Nitrae-cyclohexanediamine, its production process route is:
This route is the route of industrialization comparative maturity at present, but uses hydrogen in the production process of this route, has production safety hidden danger, and the metal catalyst using is expensive, need to develop low, the safe operational path of a kind of cost.
Summary of the invention
The object of the invention is to for deficiency of the prior art, provide low, the safe high pressure of a kind of production cost to prepare the method for Isosorbide-5-Nitrae-cyclohexanediamine.
For solving the problems of the technologies described above, the present invention adopts following technical scheme to realize:
High pressure is prepared a method for Isosorbide-5-Nitrae-cyclohexanediamine, by Isosorbide-5-Nitrae-cyclohexanediol and liquefied ammonia or 25% ammoniacal liquor under 5-20MPa high pressure, reaction 10-24h, temperature of reaction is 200 DEG C-300 DEG C, obtains target product Isosorbide-5-Nitrae-cyclohexanediamine, production line is:
The mass ratio of described Isosorbide-5-Nitrae-cyclohexanediol and liquefied ammonia is 1:1～2.
The mass ratio 1:2 of described Isosorbide-5-Nitrae-cyclohexanediol and 25% ammoniacal liquor.
As preferably, Isosorbide-5-Nitrae-cyclohexanediol to be reacted under High Temperature High Pressure with liquefied ammonia, reaction equation is:
In operational path of the present invention, under high-temperature high-voltage reaction, can form the height polymkeric substance that boils, use ammoniacal liquor to react under high-temperature and high-pressure conditions with Isosorbide-5-Nitrae-cyclohexanediol, polymer content increases, therefore use liquefied ammonia is better.
As preferably, reaction pressure is 10-15Mpa, and temperature of reaction is 220 DEG C-250 DEG C, and the reaction times is 12-14h.
Beneficial effect of the present invention: the present invention has avoided using the noble metal catalyst of price comparison costliness, and suitability for industrialized production in a large number on starting raw material Isosorbide-5-Nitrae-cyclohexanediol market, largely reduce and produce ability cost; Avoid using hydrogen simultaneously, improved the security of technique.
Embodiment
Below in conjunction with specific embodiment, the present invention is elaborated.
embodiment 1
By Isosorbide-5-Nitrae-cyclohexanediol 53g and liquefied ammonia 30g, join in 1L autoclave, control under 10-15MPa, 220 DEG C-250 DEG C reaction 12-14h of temperature, sampling analysis GC, Isosorbide-5-Nitrae-cyclohexanediamine is 95.1%, Isosorbide-5-Nitrae-cyclohexanediol 0.2%, polymkeric substance 3.8%.
embodiment 2
By Isosorbide-5-Nitrae-cyclohexanediol 116g and liquefied ammonia 60g, join in 1L autoclave, control under 10-15MPa 220 DEG C-250 DEG C reaction 12-14h of temperature, sampling analysis GC, Isosorbide-5-Nitrae-cyclohexanediamine 95.7%, Isosorbide-5-Nitrae-cyclohexanediol 0.15%, polymkeric substance 3.54%;
Take out sample, after distillation water outlet, rectification under vacuum obtains white solid Isosorbide-5-Nitrae-cyclohexanediamine 106.3g, yield 93.1%, GC purity 99.84%.
embodiment 3
By Isosorbide-5-Nitrae-cyclohexanediol 232g and liquefied ammonia 120g, join in 1L autoclave, control reaction pressure is 10-15MPa, temperature is 220 DEG C-250 DEG C, reaction 12-14h, sampling analysis GC, Isosorbide-5-Nitrae-cyclohexanediamine 96.1%, Isosorbide-5-Nitrae-cyclohexanediol 0.13%, polymkeric substance 3.04%;
Take out sample, after distillation water outlet, rectification under vacuum obtains white solid Isosorbide-5-Nitrae-cyclohexanediamine 213.4g, yield 93.5%, GC purity 99.88%.
embodiment 4
By Isosorbide-5-Nitrae-cyclohexanediol 464g and liquefied ammonia 180g, join in 1L autoclave, controlling reaction pressure is under 10-15MPa, temperature is 220 DEG C-250 DEG C, reaction 12-14h, sampling analysis GC, 1,4-cyclohexanediamine 96.4%, Isosorbide-5-Nitrae-cyclohexanediol 0.11%, polymkeric substance 3.00%;
Take out sample, after distillation water outlet, rectification under vacuum obtains white solid Isosorbide-5-Nitrae-cyclohexanediamine 430.9g, yield 94.5%, GC purity 99.83%.
Above-described embodiment is only in order to illustrate technical scheme of the present invention; but not design of the present invention and protection domain are limited; those of ordinary skill of the present invention is modified or is equal to replacement technical scheme of the present invention; and not departing from aim and the scope of technical scheme, it all should be encompassed in claim scope of the present invention.
Claims (7)
1. high pressure is prepared a method for Isosorbide-5-Nitrae-cyclohexanediamine, it is characterized in that: by 1,4-cyclohexanediol and liquefied ammonia or 25% ammoniacal liquor, under 5-20MPa high pressure, react 10-24h, and temperature of reaction is 200 DEG C-300 DEG C, obtain target product Isosorbide-5-Nitrae-cyclohexanediamine, reaction equation:
。
2. a kind of high pressure according to claim 1 is prepared the method for Isosorbide-5-Nitrae-cyclohexanediamine, it is characterized in that: the mass ratio of described Isosorbide-5-Nitrae-cyclohexanediol and liquefied ammonia is 1:1～2.
3. a kind of high pressure according to claim 1 is prepared the method for Isosorbide-5-Nitrae-cyclohexanediamine, it is characterized in that: the mass ratio 1:2 of described Isosorbide-5-Nitrae-cyclohexanediol and 25% ammoniacal liquor.
4. a kind of high pressure according to claim 1 is prepared the method for Isosorbide-5-Nitrae-cyclohexanediamine, it is characterized in that: Isosorbide-5-Nitrae-cyclohexanediol is reacted under High Temperature High Pressure with liquefied ammonia.
5. a kind of high pressure according to claim 1 is prepared the method for Isosorbide-5-Nitrae-cyclohexanediamine, it is characterized in that: reaction pressure is 10-15Mpa.
6. a kind of high pressure according to claim 1 is prepared the method for Isosorbide-5-Nitrae-cyclohexanediamine, it is characterized in that: temperature of reaction is 220 DEG C-250 DEG C.
7. a kind of high pressure according to claim 1 is prepared the method for Isosorbide-5-Nitrae-cyclohexanediamine, it is characterized in that: the reaction times is 12-14h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310483516.1A CN103896778A (en) | 2013-10-16 | 2013-10-16 | Method for preparing 1,4-cyclohexanediamine at high pressure |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310483516.1A CN103896778A (en) | 2013-10-16 | 2013-10-16 | Method for preparing 1,4-cyclohexanediamine at high pressure |
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| CN103896778A true CN103896778A (en) | 2014-07-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201310483516.1A Pending CN103896778A (en) | 2013-10-16 | 2013-10-16 | Method for preparing 1,4-cyclohexanediamine at high pressure |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001095A (en) * | 2015-06-05 | 2015-10-28 | 陈爱华 | Method for preparing 1,4-diaminocyclohexane |
| CN105237407A (en) * | 2015-11-04 | 2016-01-13 | 中国科学院青岛生物能源与过程研究所 | Preparation method of 1,2-cyclohexylenediamine |
| CN106631819A (en) * | 2016-12-20 | 2017-05-10 | 江苏清泉化学股份有限公司 | Preparation method of 1,2-cyclohexyldiamine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029367A1 (en) * | 1998-11-12 | 2000-05-25 | Lonza Ag | Method for producing cyclohexanediamines |
| WO2012113475A1 (en) * | 2011-02-21 | 2012-08-30 | Evonik Degussa Gmbh | Process for the direct amination of alcohols using ammonia to form primary amines by means of a xantphos catalyst system |
-
2013
- 2013-10-16 CN CN201310483516.1A patent/CN103896778A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029367A1 (en) * | 1998-11-12 | 2000-05-25 | Lonza Ag | Method for producing cyclohexanediamines |
| WO2012113475A1 (en) * | 2011-02-21 | 2012-08-30 | Evonik Degussa Gmbh | Process for the direct amination of alcohols using ammonia to form primary amines by means of a xantphos catalyst system |
Non-Patent Citations (1)
| Title |
|---|
| A.FISCHER,ET AL.: "Synthesis of 1,4-Diaminocyclohexane in Supercritical Ammonia", 《JOURNAL OF CATALYSIS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001095A (en) * | 2015-06-05 | 2015-10-28 | 陈爱华 | Method for preparing 1,4-diaminocyclohexane |
| CN105237407A (en) * | 2015-11-04 | 2016-01-13 | 中国科学院青岛生物能源与过程研究所 | Preparation method of 1,2-cyclohexylenediamine |
| CN106631819A (en) * | 2016-12-20 | 2017-05-10 | 江苏清泉化学股份有限公司 | Preparation method of 1,2-cyclohexyldiamine |
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Application publication date: 20140702 |