CN104492449A - Preparation method of hydrogenation catalyst and method for synthesizing DMAPA (dimethyl amionopropylamine) by applying catalyst - Google Patents
Preparation method of hydrogenation catalyst and method for synthesizing DMAPA (dimethyl amionopropylamine) by applying catalyst Download PDFInfo
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- CN104492449A CN104492449A CN201410739130.7A CN201410739130A CN104492449A CN 104492449 A CN104492449 A CN 104492449A CN 201410739130 A CN201410739130 A CN 201410739130A CN 104492449 A CN104492449 A CN 104492449A
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Abstract
The invention discloses a preparation method of a hydrogenation catalyst and a method for synthesizing DMAPA (dimethyl amionopropylamine) by applying the catalyst, wherein the hydrogenation catalyst is prepared by taking Ni, Al and auxiliaries as raw materials; the method for synthesizing DMAPA by applying the catalyst comprises the following steps: a, adding acrylonitrile into a synthetic kettle to react with dimethylamine to prepare N,N-dimethyl propionitrile; and b, adding N,N-dimethyl propionitrile into a high-pressure kettle, adding the hydrogenation catalyst and liquid ammonia, raising the temperature to 100-150 DEG C, introducing hydrogen, and maintaining the reaction temperature while stirring till the pressure in the high-pressure kettle does not decline, so as to obtain the product which is DMAPA. The preparation method of the hydrogenation catalyst disclosed by the invention is simple in process. The invention further provides the method for synthesizing DMAPA, wherein the consumption of raw materials acrylonitrile and dimethylamine can be greatly reduced and the treatment expense of a lot of hazardous wastes is lowered.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst and apply the method for this catalyst, particularly relate to a kind of preparation method of hydrogenation catalyst and apply the method for this catalyst synthesis DMAPA.
Background technology
DMAPA is a kind of important intermediate, is mainly used in surfactant, catalysts for polyurethanes, is again the raw material of preparation promoter simultaneously, itself possesses stronger antiseptic property.
The synthetic method of patent CN102617356A to DMAPA is summarized, but different with domestic production synthetic method.Main cause is domestic main to produce for the purpose of DMAPA, and the synthetic method that this patent provides is effectively to utilize for the purpose of corresponding nitrile raw material.
The catalyst that patent 200610102303.X adopts chemical synthesis to synthesize applicable nitrile hydrogenation to prepare Ni, the Co of the high selectivity of fat primary amine, auxiliary agent and rare earth metal synthesis.And this reaction system is all raw material with Arneel SD, ethanol is solvent, potash is the fat primary amine that inhibitor high-pressure hydrogenation prepares high selectivity, and its reaction system is not suitable for DMAPA production technology domestic at present.
At present, the production technology of domestic main flow is acrylonitrile and dimethylamine synthesis N, N-dimethyl propionitrile, again by N, N-dimethyl propionitrile is solvent, also be raw material, at suitable temperature and appropriate liquefied ammonia as under inhibitor, under the effect of Raney's nickel catalyst, high-pressure hydrogenation prepares thick propane diamine, and the selective at 95-96% of propane diamine prepared by current domestic propionitrile, the heavy constituent impurity of 2-3% is wherein had to produce, make domestic DMAPA device produce a large amount of heavy slags every year and need process, for professional production propane diamine device beyond doubt one very worried and waste raw material and the problem of production cost, Some Enterprises is made to have to reclaim secondary amine, but due to the ratio of secondary amine very low, heavy slag viscosity is larger, reclaim separating difficulty very large, need extra increase Technical investment and set up rectifying device to reclaim, greatly increase investment and the production operating cost of DMAPA device.
Summary of the invention
The object of the invention is to overcome DMAPA synthesizer in prior art produce every year a large amount of heavy slags need process, both wasted raw material, turn increase the defect of costs of production and operation, a kind of preparation method of hydrogenation catalyst is provided and apply this catalyst synthesis DMAPA method, preparation method's technique of hydrogenation catalyst of the present invention is simple, directly can prepare in existing equipment, be convenient to large-scale industry preparation, and the hydrogenation catalyst of preparation is applied in the method for synthesis DMAPA and effectively can improves propionitrile and prepare the selective of DMAPA, reduce synthesis material, especially the consumption of acrylonitrile, also the content of secondary amine in product is greatly reduced, avoid in product containing too much heavy slag, reduce investment and the production operating cost of DMAPA synthesizer.
In the present invention, the implication of each term is explained as follows:
DMAPA, compound N, the abbreviation of N-dimethyl-1,3-propane diamine; DEG C, temperature unit, degree Celsius.
The present invention is realized by following proposal:
A preparation method for hydrogenation catalyst, comprises the following steps:
Step one, in mass parts, takes raw material as described below,
Ni 45 ~ 55 parts
Al 43 ~ 50 parts
Auxiliary agent 2 ~ 6 parts
By after the raw material Homogeneous phase mixing that takes through high-temperature fusion, form solid alloy after cooling, then through crushing and screening, the alloyed powder of obtained 80 ~ 250 order particles;
Step 2, alloyed powder step one obtained activates in alkali lye, and then washing to pH value is 9 ~ 10, and the product of gained is hydrogenation catalyst.
Further, in step one, described auxiliary agent be one in Fe, Cr, Mo, Cu, Co, rare earth metal or several.
Further, in step one, the temperature of described high-temperature fusion is 2000 ~ 3000 DEG C.
Further, in step 2, described alkali lye to be mass fraction be 30 ~ 35% sodium hydroxide solution.
Apply a method of hydrogenation catalyst synthesis DMAPA prepared by said method, comprise the following steps,
Step a, joins acrylonitrile in synthesis reactor, is 30-80 DEG C at synthesis temperature in the kettle, stirs, under the condition of cooling water circulation cooling, drips dimethylamine, remove a small amount of dimethylamine obtain N through rectification under vacuum, N-dimethyl propionitrile in synthesis reactor;
Step b, by obtained N, N-dimethyl propionitrile adds in autoclave, adds the hydrogenation catalyst prepared, in autoclave, pass into liquefied ammonia, be warming up to 100-150 DEG C, pass into hydrogen, under agitation, pass into recirculated water and maintain reaction temperature, till in autoclave, pressure no longer declines, the product of gained is DMAPA.
Further, in step a, the mol ratio of the dimethylamine of described acrylonitrile and described dropping is 1:1 ~ 1.1.
Further, in step b, the mass ratio of described hydrogenation catalyst and described N, N-dimethyl propionitrile is 1:10 ~ 30.
Beneficial effect of the present invention is:
1. the invention provides a kind of preparation method of hydrogenation catalyst, there is technique simple, and on Raney's nickel catalyst production equipment, easily carry out the advantage of synthesizing, be easy to the stable in properties that realizes often criticizing catalyst and homogeneous according to fixing rate of charge;
2. the present invention also provides a kind of method of synthesizing DMAPA, the method applies foregoing hydrogenation catalyst, in operating cost, use this hydrogenation catalyst can greatly reduce the consumption of raw material propylene nitrile and dimethylamine, save the consumption of raw materials cost of DMAPA synthesizer, greatly reduce the output of unit weight slag simultaneously, save the disposal cost that a large amount of danger is useless.
Accompanying drawing explanation
Fig. 1 is the preparation method of a kind of hydrogenation catalyst of the present invention and applies the process chart of method of this catalyst synthesis DMAPA.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described:
Embodiment 1
In mass parts, take raw material as described below, Ni:50 part; Al:46 part; Co:1.5 part; La:0.2 part; Cr:1.0 part; Fe:0.8 part; Mo:0.5 part, by after the raw material Homogeneous phase mixing taken at temperature is 3000 DEG C high-temperature fusion, form solid alloy after cooling under nitrogen protection, then through crushing and screening, the alloyed powder of obtained 80 ~ 150 order particles; Activate in the sodium hydroxide solution of 30%, remove most Al in alloyed powder, then spending deionized water to pH value is 9 ~ 10, and the product of gained is hydrogenation catalyst.
Acrylonitrile is joined in synthesis reactor, be 50 DEG C in temperature, stir, under the condition of cooling water circulation cooling, in synthesis reactor, drip dimethylamine, wherein, the mol ratio of the dimethylamine of acrylonitrile and dropping is 1:1, removes a small amount of dimethylamine obtain N through rectification under vacuum, N-dimethyl propionitrile;
Get the N that 1000 g are obtained, N-dimethyl propionitrile adds in 2000 ml autoclaves, add the hydrogenation catalyst that 50 g prepare, again autoclave is sealed, liquefied ammonia is passed in autoclave, be warming up to 100 DEG C, interval passes into hydrogen, maintaining reacting kettle inner pressure is below 3.0MPa, under agitation, pass into recirculated water and maintain reaction temperature, till in autoclave, pressure no longer declines, judge that reaction terminates, get reactant liquor in reactor to detect, DMAPA content 97.9%, propionitrile residual volume 0.05%, light component impurity content 1.45%, heavy constituent impurity content 1.05%, wherein, secondary amine 0.51%.
Embodiment 2
In mass parts, take raw material as described below, Ni:48 part; Al:48 part; Co:1.5 part; La:0.2 part; Cr:1.0 part; Fe:0.8 part; Mo:0.5 part, by after the raw material Homogeneous phase mixing taken at temperature is 2500 DEG C high-temperature fusion, form solid alloy after cooling under nitrogen protection, then through crushing and screening, the alloyed powder of obtained 120 ~ 250 order particles; Activate in the sodium hydroxide solution of 30%, remove most Al in alloyed powder, then spending deionized water to pH value is 9 ~ 10, and the product of gained is hydrogenation catalyst.
Acrylonitrile is joined in synthesis reactor, be 50 DEG C in temperature, stir, under the condition of cooling water circulation cooling, in synthesis reactor, drip dimethylamine, wherein, the mol ratio of the dimethylamine of acrylonitrile and dropping is 1:1, removes a small amount of dimethylamine obtain N through rectification under vacuum, N-dimethyl propionitrile;
Get the N that 500 g are obtained, N-dimethyl propionitrile adds in 100 ml autoclaves, add the hydrogenation catalyst that 25 g prepare, again autoclave is sealed, liquefied ammonia is passed in autoclave, be warming up to 100 DEG C, interval passes into hydrogen, maintaining reacting kettle inner pressure is below 3.0MPa, under agitation, pass into recirculated water and maintain reaction temperature, till in autoclave, pressure no longer declines, judge that reaction terminates, get reactant liquor in reactor to detect, EMAPA content 97.5%, propionitrile residual volume 0.07%, light component impurity content 1.38%, heavy constituent impurity content 1.05%, wherein, secondary amine 0.5%.
Embodiment 3
In mass parts, take raw material as described below, Ni:49 part; Al:45 part; Co:2 part; La:0.5 part; Cr:1.5 part; Fe:1 part; Mo:1 part, by after the raw material Homogeneous phase mixing taken at temperature is 2800 DEG C high-temperature fusion, form solid alloy after cooling under nitrogen protection, then through crushing and screening, the alloyed powder of obtained 120 ~ 250 order particles; Activate in the sodium hydroxide solution of 30%, remove most Al in alloyed powder, then spending deionized water to pH value is 9 ~ 10, and the product of gained is hydrogenation catalyst.
Acrylonitrile is joined in synthesis reactor, be 50 DEG C in temperature, stir, under the condition of cooling water circulation cooling, in synthesis reactor, drip dimethylamine, wherein, the mol ratio of the dimethylamine of acrylonitrile and dropping is 1:1, removes a small amount of dimethylamine obtain N through rectification under vacuum, N-dimethyl propionitrile;
Get the N that 1000 g are obtained, N-dimethyl propionitrile adds in 2000 ml autoclaves, add the hydrogenation catalyst that 50 g prepare, again autoclave is sealed, liquefied ammonia is passed in autoclave, be warming up to 100 DEG C, interval passes into hydrogen, maintaining reacting kettle inner pressure is below 3.0MPa, under agitation, pass into recirculated water and maintain reaction temperature, till in autoclave, pressure no longer declines, judge that reaction terminates, get reactant liquor in reactor to detect, DMAPA content 98.1%, propionitrile residual volume 0.03%, light component impurity content 0.98%, heavy constituent impurity content 0.89%, wherein, secondary amine 0.45%.
Embodiment 4
In mass parts, take raw material as described below, Ni:53 part; Al:44 part; Co:1 part; La:0.2 part; Cr:1.0 part; Fe:0.5 part; Mo:0.3 part, by after the raw material Homogeneous phase mixing taken at temperature is 2400 DEG C high-temperature fusion, form solid alloy after cooling under nitrogen protection, then through crushing and screening, the alloyed powder of obtained 120 ~ 250 order particles; Activate in the sodium hydroxide solution of 30%, remove most Al in alloyed powder, then spending deionized water to pH value is 9 ~ 10, and the product of gained is hydrogenation catalyst.
Acrylonitrile is joined in synthesis reactor, be 50 DEG C in temperature, stir, under the condition of cooling water circulation cooling, in synthesis reactor, drip dimethylamine, wherein, the mol ratio of the dimethylamine of acrylonitrile and dropping is 1:1, removes a small amount of dimethylamine obtain N through rectification under vacuum, N-dimethyl propionitrile;
Get the N that 600 g are obtained, N-dimethyl propionitrile adds in 1000 ml autoclaves, add the hydrogenation catalyst that 50 g prepare, again autoclave is sealed, liquefied ammonia is passed in autoclave, be warming up to 100 DEG C, interval passes into hydrogen, maintaining reacting kettle inner pressure is below 3.0MPa, under agitation, pass into recirculated water and maintain reaction temperature, till in autoclave, pressure no longer declines, judge that reaction terminates, get reactant liquor in reactor to detect, DMAPA content 97.6%, propionitrile residual volume 0.01%, light component impurity content 1.35%, heavy constituent impurity content 1.04%, wherein, secondary amine 0.48%.
Although done comparatively detailed elaboration to technical scheme of the present invention and enumerated; be to be understood that; to those skilled in the art; amendment is made to above-described embodiment or adopts equivalent replacement scheme; this is apparent to those skilled in the art; these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (7)
1. a preparation method for hydrogenation catalyst, is characterized in that, comprises the following steps:
Step one, in mass parts, takes raw material as described below,
Ni 45 ~ 55 parts
Al 43 ~ 50 parts
Auxiliary agent 2 ~ 6 parts
By after the raw material Homogeneous phase mixing that takes through high-temperature fusion, form solid alloy after cooling, then through crushing and screening, the alloyed powder of obtained 80 ~ 250 order particles;
Step 2, alloyed powder step one obtained activates in alkali lye, and then washing to pH value is 9 ~ 10, and the product of gained is hydrogenation catalyst.
2. the preparation method of a kind of hydrogenation catalyst according to claim 1, is characterized in that, in step one, described auxiliary agent be one in Fe, Cr, Mo, Cu, Co, rare earth metal or several.
3. the preparation method of hydrogenation catalyst according to claim 1, is characterized in that, in step one, the temperature of described high-temperature fusion is 2000 ~ 3000 DEG C.
4. the preparation method of a kind of hydrogenation catalyst according to claim 1, is characterized in that, in step 2, described alkali lye to be mass fraction be 30 ~ 35% sodium hydroxide solution.
5. the hydrogenation catalyst that described in application rights requirement 1 prepared by preparation method synthesizes a method of DMAPA, it is characterized in that, comprises the following steps,
Step a, joins acrylonitrile in synthesis reactor, is 30-80 DEG C at synthesis temperature in the kettle, stirs, under the condition of cooling water circulation cooling, drips dimethylamine, remove a small amount of dimethylamine obtain N through rectification under vacuum, N-dimethyl propionitrile in synthesis reactor;
Step b, by obtained N, N-dimethyl propionitrile adds in autoclave, adds the hydrogenation catalyst prepared, in autoclave, pass into liquefied ammonia, be warming up to 100-150 DEG C, pass into hydrogen, under agitation, pass into recirculated water and maintain reaction temperature, till in autoclave, pressure no longer declines, the product of gained is DMAPA.
6. the method for synthesis DMAPA according to claim 5, it is characterized in that, in step a, the mol ratio of the dimethylamine of described acrylonitrile and described dropping is 1:1 ~ 1.1.
7. the method for synthesis DMAPA according to claim 5, it is characterized in that, in step b, the mass ratio of described hydrogenation catalyst and described N, N-dimethyl propionitrile is 1:10 ~ 30.
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Cited By (5)
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| CN105198754A (en) * | 2015-09-15 | 2015-12-30 | 浙江希尔化工股份有限公司 | Method for preparing N,N-dimethyl-1,3-diaminopropane |
| CN110252322A (en) * | 2019-07-05 | 2019-09-20 | 安徽天择化工有限公司 | A kind of quaternary Raney nickel, preparation method and its application |
| CN113200870A (en) * | 2021-05-07 | 2021-08-03 | 大连理工大学 | Process for continuously preparing N, N-dimethyl-1, 3-propane diamine by using micro-mixing and fixed bed reactor |
| CN113620813A (en) * | 2021-08-13 | 2021-11-09 | 中国天辰工程有限公司 | Preparation method of N, N-dimethyl-1, 3-propane diamine |
| CN113896654A (en) * | 2021-06-24 | 2022-01-07 | 万华化学集团股份有限公司 | Method for producing DMAPA and co-producing bis-DMAPA and tri-DMAPA |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105198754A (en) * | 2015-09-15 | 2015-12-30 | 浙江希尔化工股份有限公司 | Method for preparing N,N-dimethyl-1,3-diaminopropane |
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| CN113896654A (en) * | 2021-06-24 | 2022-01-07 | 万华化学集团股份有限公司 | Method for producing DMAPA and co-producing bis-DMAPA and tri-DMAPA |
| CN113896654B (en) * | 2021-06-24 | 2023-09-19 | 万华化学集团股份有限公司 | Method for producing DMAPA and co-producing bis-DMAPA and tri-DMAPA |
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Application publication date: 20150408 |