CN102344373A - Method for preparing 2-methyl, 5-pentamethylenediamine - Google Patents
Method for preparing 2-methyl, 5-pentamethylenediamine Download PDFInfo
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- CN102344373A CN102344373A CN2011103091969A CN201110309196A CN102344373A CN 102344373 A CN102344373 A CN 102344373A CN 2011103091969 A CN2011103091969 A CN 2011103091969A CN 201110309196 A CN201110309196 A CN 201110309196A CN 102344373 A CN102344373 A CN 102344373A
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- isophthalic acid
- methyl isophthalic
- hydrogen
- methyl
- catalyzer
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Abstract
The invention relates to a method for preparing 2-methyl, 5-pentamethylenediamine, which is characterized in that: 2-methyl, 5-glutaronitrile is adopted as a raw material, and Co-Mo/gamma-A12O3 catalyst is adopted as catalyst and comprises the following compositions: 1.0-50.0 percent of Co, 0.005-0.3 percent of Pt, 0.1-5.0 percent of Mo, and the balance of gamma-A12O3; and the reaction is carried out in a gas phase by adopting a continuous process, and the specific operating conditions are as follows: pressure: ordinary pressure-10MPa, temperature: 100-320 DEG C, liquid-state airspeed of dinitrile: 0.2-2.0h<-1>, molar ratio of cyanamide: 1.0-8.0, molar ratio of hydrogen-nitrile: 5-50, and catalyst amount: 0.1-2.0m<3>nitrile/(hr.m<3> catalyst). The 2-methyl, 5- glutaronitrile is fed into a preheater to be mixed, preheat and vaporized with ammonia gas and hydrogen and then enters a fixed bed reactor to be reacted, a reacted material is subjected to condensation, cooling and gas-liquid separation to enter a distillation refining process, the 2-methyl, 5-pentamethylenediamine is produced as a product, and bits of diethylenetriamine is produced due to side reaction. The method provided by the invention has a simple process flow, high conversion rate, good selectivity, less byproducts and low production cost of the product.
Description
Technical field
The present invention relates to a kind of chemical synthesis process, especially a kind of with the 2-methyl isophthalic acid, the 5-trimethylene cyanide is the 2-methyl isophthalic acid of raw material, the preparation method of 5-pentamethylene diamine.
Background technology
2-methyl isophthalic acid, 5-pentamethylene diamine are a kind of important chainextenders during spandex fiber spandex, high modulus fibre aramid fiber are produced, simultaneously also as fields such as epoxy curing agents.Industrial production mainly adopts the Methionin decarboxylation and gets, and production cost is high, and side reaction is many; Prepared in laboratory is raw material with the trimethylene cyanide, adopts liquid phase reaction, after the ethanol solution of trimethylene cyanide is boiled, is reductive agent with the sodium Metal 99.5, adds entry after having reacted, and ethanol is steamed, and remaining reactants is distilled with superheated vapour.Overhead product neutralizes with dilute hydrochloric acid; Evaporate to dryness, residuum neutralize with potassium hydroxide with absolute ethanol washing again; Boil off water; Underpressure distillation gets the product pentamethylene diamine, and this technology is because reaction scheme is long; The waste water and dregs quantity discharged is big; The sodium speed of response is violent, and system temperature is difficult to control, so there is not industrialized unit to use.
Summary of the invention
It is high to the purpose of this invention is to provide a kind of transformation efficiency, and selectivity is good, and flow process is simple, and production cost is low, is fit to industrial 2-methyl isophthalic acid, 5 pentamethylene diamine preparing methods.Its technical scheme is:
A kind of 2-methyl isophthalic acid, the preparation method of 5 pentamethylene diamines is characterized in that:
1) with the 2-methyl isophthalic acid, the 5-trimethylene cyanide is a raw material, with Co-Mo/ γ-Al
2O
3Be catalyzer, wherein the mass ratio of catalyzer composition is: Co is 1.0～50.0%, and Pt is 0.005～0.3%, and Mo is 0.1～5.0%, and all the other are γ-Al
2O
3
2) this is reflected at gas phase and carries out; Adopt the continous way process, with the 2-methyl isophthalic acid, the 5-trimethylene cyanide is squeezed into preheater by volume pump; Then with ammonia, hydrogen mix preheating vaporization in material mixer after; Reaching the cyanamide mol ratio is 1.0～8.0, and hydrogen nitrile mol ratio is 5～50, gets into the fixed-bed reactor reaction again; Reaction conditions is: pressure 0.1～10Mpa; 100～320 ℃ of temperature, the 2-methyl isophthalic acid, 5-trimethylene cyanide air speed is 0.2～2.0h
-1, and the flow of reactor for every cubic metre of catalyzer per hour through 0.1～2.0m
3
3) reaction product is cooled off and gas-liquid separation; Gas phase after the separation is compressed incoming stock mixing tank through recycle compressor; Liquid phase get into rectifying tower separate purify the 2-methyl isophthalic acid; The 5-pentamethylene diamine, unreacted ammonia, 2-methyl isophthalic acid in the liquid phase, the 5-trimethylene cyanide turns back to material mixer; And the ammonia of supplement consumed, hydrogen and 2-methyl isophthalic acid; The 5-trimethylene cyanide, keeping the cyanamide mol ratio is 1.0～8.0, hydrogen nitrile mol ratio is 5～50.
Described 2-methyl isophthalic acid, the preparation method of 5-pentamethylene diamine, the preparation procedures system is carried out closed cycle, material recycle.
The present invention compared with prior art, its advantage is: with the 2-methyl isophthalic acid, the 5-trimethylene cyanide is raw material continuous catalytic hydrogenation Synthetic 2-methyl isophthalic acid, the 5-pentamethylene diamine.Present method technical process is simple, and transformation efficiency is high, and selectivity is good, and by product is few, and separation process is simple and clear, and energy consumption, raw material consumption are low, and the products production cost is low.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1:
1) with the 2-methyl isophthalic acid, the 5-trimethylene cyanide is a raw material, with Co-Mo/ γ-Al
2O
3Be catalyzer, the mass ratio that catalyzer is formed is: Co is 1.0%, and Pt is 0.3%, and Mo is 5.0%, and all the other are γ-Al
2O
3, catalyzer is numbered A1.
2) this is reflected at gas phase and carries out; Adopt the continous way process, with the 2-methyl isophthalic acid, the 5-trimethylene cyanide is squeezed into preheater by volume pump; Then with ammonia, hydrogen mix preheating vaporization in material mixer after; Reaching the cyanamide mol ratio is 3.0, and hydrogen nitrile mol ratio is 10, gets into the fixed-bed reactor reaction again; Reaction conditions is: pressure 3Mpa; 220 ℃ of temperature, the 2-methyl isophthalic acid, 5-trimethylene cyanide air speed is 1.0h
-1, and pass through 1.4m for every cubic metre of catalyzer per hour at the flow of reactor
3
3) reaction product is cooled off and gas-liquid separation; Gas phase after the separation is compressed incoming stock mixing tank through recycle compressor; Liquid phase get into rectifying tower separate purify the 2-methyl isophthalic acid; The 5-pentamethylene diamine, unreacted ammonia, 2-methyl isophthalic acid in the liquid phase, the 5-trimethylene cyanide turns back to material mixer; And the ammonia of supplement consumed, hydrogen and 2-methyl isophthalic acid; The 5-trimethylene cyanide, keeping the cyanamide mol ratio is 3.0, hydrogen nitrile mol ratio is 10.
Embodiment 2: the mass ratio that catalyzer is formed is: Co is 50.0%, and Pt is 0.005%, and Mo is 0.1%, and all the other are γ-Al
2O
3, catalyzer is numbered A2.
Embodiment 3: the mass ratio that catalyzer is formed is: Co is 20.0%, and Pt is 0.1%, and Mo is 1.0%, and all the other are γ-Al
2O
3, catalyzer is numbered A3.
Embodiment 4: the mass ratio that catalyzer is formed is: Co is 40.0%, and Pt is 0.2%, and Mo is 2.0%, and all the other are γ-Al
2O
3, catalyzer is numbered A4.
Embodiment 5: the mass ratio that catalyzer is formed is: Co is 30.0%, and Pt is 0.3%, and Mo is 4.0%, and all the other are γ-Al
2O
3, catalyzer is numbered A5.
Embodiment 1---embodiment 5: with the catalyzer diameter of packing into is 32 * 3mm, the stainless steel reactor of length 1450mm.The stainless steel temperature-measuring casing of ∮ 8 * 1mm is set in the reactor, and catalyst packing height is 850mm, and loaded catalyst is 400ml.Reaction raw materials is to go out under enterprising, gets into the separator vapor phase ammonia, hydrogen discharge from the separator top, bottom liquid phases timing sampling through condensation cooling back from the effusive material of reactor bottom.Form with gas chromatographic analysis, concrete reaction conditions and result list in table 1.
Table 1. reaction conditions and result
Can know by data in the table 1, under present inventor's processing condition, react that the result all has higher transformation efficiency and selectivity preferably.
Embodiment 6: according to example 1～5 said device, flow process, filling 400ml is numbered the catalyzer of A4, carries out 240 hours stable service tests.Reaction pressure: 3.0MPa, temperature: 220 ℃, nitrile liquid hourly space velocity: 1.0h
-1, the cyanamide mol ratio: 5, hydrogen nitrile mol ratio: 10, form with gas chromatographic analysis, concrete reaction conditions and result list in table 2.
Table 2.240 hour stable service test
Can be known that by table 2 data under these processing condition, the transformation efficiency of reaction is higher than 95%, selectivity is higher than 98%, and catalyzer has stability preferably simultaneously.
Claims (2)
1. 2-methyl isophthalic acid, the preparation method of 5-pentamethylene diamine is characterized in that:
1) with the 2-methyl isophthalic acid, the 5-trimethylene cyanide is a raw material, with Co-Mo/ γ-Al
2O
3Be catalyzer, wherein Co-Mo/ γ-Al
2O
3The mass ratio that catalyzer is formed is: Co is 1.0～50.0%, and Pt is 0.005～0.3%, and Mo is 0.1～5.0%, and all the other are γ-Al
2O
3
2) this is reflected at gas phase and carries out; Adopt the continous way process; With the 2-methyl isophthalic acid; The 5-trimethylene cyanide is squeezed into preheater by volume pump; Then with ammonia, hydrogen mix preheating vaporization in material mixer after; Reaching the cyanamide mol ratio is 1.0～8.0; Hydrogen nitrile mol ratio is 5～50; Get into the fixed-bed reactor reaction again; Reaction conditions is: pressure 0.1～10Mpa; 100～320 ℃ of temperature, the 2-methyl isophthalic acid, 5-trimethylene cyanide air speed be 0.2～2.0h1 and the flow of reactor for every cubic metre of catalyzer per hour through 0.1～2.0m
3
3) reaction product is cooled off and gas-liquid separation; Gas phase after the separation is compressed incoming stock mixing tank through recycle compressor; Liquid phase get into rectifying tower separate purify the 2-methyl isophthalic acid; The 5-pentamethylene diamine, unreacted ammonia, 2-methyl isophthalic acid in the liquid phase, the 5-trimethylene cyanide turns back to material mixer; And the ammonia of supplement consumed, hydrogen and 2-methyl isophthalic acid; The 5-trimethylene cyanide, keeping the cyanamide mol ratio is 1.0～8.0, hydrogen nitrile mol ratio is 5～50.
2. 2-methyl isophthalic acid according to claim 1, the preparation method of 5-pentamethylene diamine is characterized in that: the preparation procedures system is carried out closed cycle, material recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103091969A CN102344373A (en) | 2011-09-30 | 2011-09-30 | Method for preparing 2-methyl, 5-pentamethylenediamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103091969A CN102344373A (en) | 2011-09-30 | 2011-09-30 | Method for preparing 2-methyl, 5-pentamethylenediamine |
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|---|---|
| CN102344373A true CN102344373A (en) | 2012-02-08 |
Family
ID=45543491
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103091969A Pending CN102344373A (en) | 2011-09-30 | 2011-09-30 | Method for preparing 2-methyl, 5-pentamethylenediamine |
Country Status (1)
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106536476A (en) * | 2014-04-25 | 2017-03-22 | 因温斯特技术公司 | Preparation of diamines by hydrogenation of dinitriles |
| CN107365257A (en) * | 2017-08-02 | 2017-11-21 | 厦门大学 | A kind of 2 methyl cellosolve acetate glutaronitrile Hydrogenation for 2 making methylpentamethylenediamine diamines and 3 methyl piperidines method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4885391A (en) * | 1988-01-14 | 1989-12-05 | E. I. Du Pont De Nemours And Company | Production of C4 to C12 amines |
| DE102007011484A1 (en) * | 2007-03-07 | 2008-09-11 | Evonik Degussa Gmbh | Process for the preparation of trimethylhexamethylenediamine |
| WO2009121704A1 (en) * | 2008-03-31 | 2009-10-08 | Rhodia Operations | Method for making methylpentamethylene diamine and methylpiperidine |
| CN101619025A (en) * | 2009-07-29 | 2010-01-06 | 浙江新化化工股份有限公司 | Continuous preparation method for n-pentylamine |
-
2011
- 2011-09-30 CN CN2011103091969A patent/CN102344373A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4885391A (en) * | 1988-01-14 | 1989-12-05 | E. I. Du Pont De Nemours And Company | Production of C4 to C12 amines |
| DE102007011484A1 (en) * | 2007-03-07 | 2008-09-11 | Evonik Degussa Gmbh | Process for the preparation of trimethylhexamethylenediamine |
| WO2009121704A1 (en) * | 2008-03-31 | 2009-10-08 | Rhodia Operations | Method for making methylpentamethylene diamine and methylpiperidine |
| CN101619025A (en) * | 2009-07-29 | 2010-01-06 | 浙江新化化工股份有限公司 | Continuous preparation method for n-pentylamine |
Non-Patent Citations (2)
| Title |
|---|
| S. LANINI, R. PRINS等: "Synthesis of/3-picoline from 2-methylglutaronitrile over supported noble metal catalysts I. Catalyst activity and selectivity", 《APPLIED CATALYSIS A》 * |
| 李崇等: "非晶态镍催化剂上戊二腈催化加氢制备戊二胺", 《石油化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106536476A (en) * | 2014-04-25 | 2017-03-22 | 因温斯特技术公司 | Preparation of diamines by hydrogenation of dinitriles |
| CN106536476B (en) * | 2014-04-25 | 2018-11-13 | 英威达纺织（英国）有限公司 | Diamines is prepared by making dinitrile hydrogenation |
| CN107365257A (en) * | 2017-08-02 | 2017-11-21 | 厦门大学 | A kind of 2 methyl cellosolve acetate glutaronitrile Hydrogenation for 2 making methylpentamethylenediamine diamines and 3 methyl piperidines method |
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Application publication date: 20120208 |