CN103664634A - Supported catalyst for preparation of 1, 2-propane diamine - Google Patents
Supported catalyst for preparation of 1, 2-propane diamine Download PDFInfo
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- CN103664634A CN103664634A CN201210325806.9A CN201210325806A CN103664634A CN 103664634 A CN103664634 A CN 103664634A CN 201210325806 A CN201210325806 A CN 201210325806A CN 103664634 A CN103664634 A CN 103664634A
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- propylene diamine
- catalyzing
- synthesizing
- propylene
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Abstract
The invention discloses a supported catalyst for preparation of 1, 2-propane diamine through catalysis. The 1, 2-propane diamine is prepared by a method comprising main synthesis steps of adding 1, 2-propylene dichloride, ammonia water, and the supported catalyst into a reaction kettle; rotating the reaction kettle in a homogeneous phase reactor at constant speed; carrying out amination at reaction temperature of 140 DEG C-170 DEG C so as to prepare the 1, 2-propane diamine, wherein the yield of the 1, 2-propane diamine is more than 65%; and after reaction, firstly removing unreacted ammonia gas, and then distilling at normal pressure so as to obtain a 1, 2-propane diamine aqueous solution. The supported catalyst has the advantages that the yield of the 1, 2-propane diamine prepared by catalysis of the supported catalyst is relatively high; the byproduct 1, 2-propylene dichloride generated in production of chloropropene is taken as the raw material, so that the production cost is greatly lowered; the reaction process is simple, the operation is convenient; the method is safe and environment-friendly and is beneficial to industrial production.
Description
Technical field:
The invention belongs to chemosynthesis technical field, relate to the preparation of a class loaded catalyst, and carry out catalyzing and synthesizing of 1,2-propylene diamine with this catalyzer.
Technical background:
1,2-propylene diamine is a kind of important organic chemical industry's intermediate and raw material, and the content of application aspect comprises for the production of beneficiation reagent, as metal passivator, production aviation resin curing agent; When producing thiofide, also there is certain use value; Simultaneously 1,2-propylene diamine is also for the reagent (the calibrating aspects of the elements such as mercury, copper and silver) of dyestuff, plating and analysis metal; For the production of 1,2-trimethylenedinitrilo-tertraacetic acid; Use aspect pharmacy, comprises as the intermediate of producing the anticarcinogen of tetrahydroform.
At present, along with the expansion gradually of 1,2-propylene diamine range of application, its market demand also increases thereupon.The demand in the whole world reaches thousands of tons of.Up to the present, domestic 1,2-propylene diamine product major part is from BASF import.Domestic traditional technique is that raw material synthesizes 1,2-propylene dichloride by amination reaction with 1,2-propylene dichloride, known to applicant, adopts the product yield of this route all lower than 50%.
Adopt the lower reason of propylene dichloride reaction yield to be that granular specific surface area of catalyst is less, the avtive spot providing is less.Cause when reaction not fully, rapidly, caused more side reaction.By catalyst activity component is dispersed in and is had compared with on the carrier of bigger serface, improved on the whole the catalytic activity of catalyzer, be conducive to react Raw transformation efficiency and optionally improve.
Summary of the invention
The present invention has prepared a class loaded catalyst, is intended to, by means of the larger specific surface area of carrier, make catalyst activity component be scattered in surface, has increased the dispersity of catalytic active component, has increased the avtive spot of catalysis simultaneously.Utilize this catalyst 1,2-propylene dichloride carries out amination reaction and prepares 1,2-propylene diamine.This catalyzer has higher catalytic activity, has improved to a great extent the yield of product.
The process of this experiment is: 1,2-propylene dichloride, ammoniacal liquor, loaded catalyst are joined in reactor, and reactor is at the uniform velocity rotation in homogeneous reactor, at 140 ℃～170 ℃, reacts 1h～4h.Reaction equation is as follows:
The active ingredient of described catalyzer is CuO, and its carrier is selected nanometer or micron order SiO
2, TiO
2, Al
2o
3, ZrO
2powder or their mixture, the shared ratio of active ingredient is 5%～20%.By dipper precipitation method, coprecipitation method, sol-gel method, hydrolytic precipitation method, hydrothermal method, reverse micelle method, spray method, be prepared, then drying, calcining and a kind of black powder shape catalyzer of preparing.
Described 1, the mol ratio of 2-propylene dichloride and ammonia is 1: 10～40, and the consumption of catalyzer is 1%～20% of 1,2-propylene dichloride quality.
Temperature of reaction of the present invention is 140 ℃～170 ℃; Reaction times is 1h～4h.
The present invention compares with existing technique, has the following advantages: 1,2-propylene diamine is prepared in (1) loaded catalyst catalysis, has obtained higher yield; (2) adopt and produce the by product 1 producing in propenyl chloride process, 2-propylene dichloride is raw material, has reduced greatly production cost; (3) reaction process is simple, easy to operate; (4) present method safety and environmental protection, is beneficial to suitability for industrialized production.
Embodiment:
Reference examples 1
In reactor, add 10mL1,2-propylene dichloride, 0.05g CuO, 100mL ammoniacal liquor.Reactor is put into homogeneous reactor and at the uniform velocity rotate, be warming up to 160 ℃ and keep 3h.Be cooled to room temperature, remove unreacted ammonia, gas-chromatography detects, and the yield of 1,2-propylene diamine is 40%.
Reference examples 2
In reactor, add 5mL1,2-propylene dichloride, 0.5g CuO, 100mL ammoniacal liquor.Reactor is put into homogeneous reactor and at the uniform velocity rotate, be warming up to 160 ℃ and keep 3h.Be cooled to room temperature, remove unreacted ammonia, gas-chromatography detects, and the yield of 1,2-propylene diamine is 47.05%.
Embodiment 1
Accurately take 1g SiO
2be suspended in 20mL distilled water, then taken 0.3196g CuCl
22H
2o, is joined in suspension, by the ultrasonic 30min of this mixed solution with this by SiO
2disperse uniformly.Mixed solution heating and thermal insulation under the condition of 100 ℃ after ultrasonic, until then solution evaporate to dryness transfers them in thermostat container and be incubated 2h under the condition of 120 ℃, is finally transferred in retort furnace and calcine 3h at 400 ℃.The Catalysts Cu O/SiO that this prepares
2for ensuing catalyzed reaction.Wherein the content of CuO is 15% of carrier quality.In reactor, add 5mL 1,2-propylene dichloride, 0.5g CuO/SiO
2, 100mL ammoniacal liquor.Reactor is put into homogeneous reactor and at the uniform velocity rotate, be warming up to 160 ℃ and keep 3h.Be cooled to room temperature, remove unreacted ammonia, gas-chromatography detects, and the yield of 1,2-propylene diamine is 64.72%.
Embodiment 2
Accurately take 1g TiO
2be suspended in 20mL distilled water, then taken 0.3196g CuCl
22H
2o, is joined in suspension, by the ultrasonic 30min of this mixed solution with this by TiO
2disperse uniformly.Mixed solution heating and thermal insulation under the condition of 100 ℃ after ultrasonic, until then solution evaporate to dryness transfers them in thermostat container and be incubated 2h under the condition of 120 ℃, is finally transferred in retort furnace and calcine 3h at 400 ℃.The Catalysts Cu O/TiO that this prepares
2for ensuing catalyzed reaction.Wherein the content of CuO is 15% of carrier quality.In reactor, add 5mL 1,2-propylene dichloride, 0.5g CuO/TiO
2, 100mL ammoniacal liquor.Reactor is put into homogeneous reactor and at the uniform velocity rotate, be warming up to 160 ℃ and keep 3h.Be cooled to room temperature, remove unreacted ammonia, gas-chromatography detects, and the yield of 1,2-propylene diamine is 66.03%.
Embodiment 3
Accurately take 1g Al
2o
3be suspended in 20mL distilled water, then taken 0.3196g CuCl
22H
2o, is joined in suspension, by the ultrasonic 30min of this mixed solution with this by Al
2o
3disperse uniformly.Mixed solution heating and thermal insulation under the condition of 100 ℃ after ultrasonic, until then solution evaporate to dryness transfers them in thermostat container and be incubated 2h under the condition of 120 ℃, is finally transferred in retort furnace and calcine 3h at 400 ℃.The Catalysts Cu O/Al that this prepares
2o
3for ensuing catalyzed reaction.Wherein the content of CuO is 15% of carrier quality.In reactor, add 5mL 1,2-propylene dichloride, 0.5gCuO/Al
2o
3, 100mL ammoniacal liquor.Reactor is put into homogeneous reactor and at the uniform velocity rotate, be warming up to 160 ℃ and keep 3h.Be cooled to room temperature, remove unreacted ammonia, gas-chromatography detects, and the yield of 1,2-propylene diamine is 68.39%.
Embodiment 4
Accurately take 1g ZrO
2be suspended in 20mL distilled water, then taken 0.3196g CuCl
22H
2o, is joined in suspension, by the ultrasonic 30min of this mixed solution with this by ZrO
2disperse uniformly.Mixed solution heating and thermal insulation under the condition of 100 ℃ after ultrasonic, until then solution evaporate to dryness transfers them in thermostat container and be incubated 2h under the condition of 120 ℃, is finally transferred in retort furnace and calcine 3h at 400 ℃.The Catalysts Cu O/ZrO that this prepares
2for ensuing catalyzed reaction.Wherein the content of CuO is 15% of carrier quality.In reactor, add 5mL 1,2-propylene dichloride, 0.5gCuO/ZrO
2, 100mL ammoniacal liquor.Reactor is put into homogeneous reactor and at the uniform velocity rotate, be warming up to 160 ℃ and keep 3h.Be cooled to room temperature, remove unreacted ammonia, gas-chromatography detects, and the yield of 1,2-propylene diamine is 66.16%.
Claims (9)
1. a process for catalytic synthesis for 2-propylene diamine, is characterized in that: with 1,2-propylene dichloride for raw material, in reactor, add ammoniacal liquor, loaded catalyst simultaneously, at 140 ℃～170 ℃ of temperature, carry out synthetic 1, the 2-propylene diamine of amination reaction, its reaction equation is as follows:
2. as claimed in claim 11, catalyzing and synthesizing of 2-propylene diamine, is characterized in that: the mol ratio of 1,2-propylene dichloride and ammonia is 1: 10～40.
3. as claimed in claim 11, catalyzing and synthesizing of 2-propylene diamine, is characterized in that: in the first step, the consumption of catalyzer is 1%～20% of 1,2-propylene dichloride quality.
As described in claim 1 or 31, catalyzing and synthesizing of 2-propylene diamine, is characterized in that: described catalyzer is to take CuO as active ingredient, with SiO
2, TiO
2, Al
2o
3, ZrO
2for carrier, its carrier is selected nanometer or micron order SiO
2, TiO
2, Al
2o
3, ZrO
2powder or their mixture, be prepared by dipper precipitation method, coprecipitation method, sol-gel method, hydrolytic precipitation method, hydrothermal method, reverse micelle method, spray method, then drying, calcining and a kind of black powder shape catalyzer of preparing.
As described in claim 1 or 3 or 41, catalyzing and synthesizing of 2-propylene diamine, is characterized in that: in described catalyzer, the consumption of active ingredient CuO is 5%～20% of carrier quality.
As described in claim 1 or 3 or 41, catalyzing and synthesizing of 2-propylene diamine, is characterized in that: the calcining temperature of described catalyzer is 200 ℃～500 ℃.
As described in claim 1 or 3 or 41, catalyzing and synthesizing of 2-propylene diamine, is characterized in that: the calcination time of described catalyzer is 2h～5h.
8. as claimed in claim 11, catalyzing and synthesizing of 2-propylene diamine, is characterized in that: temperature of reaction is 140 ℃～170 ℃.
9. as claimed in claim 11, catalyzing and synthesizing of 2-propylene diamine, is characterized in that: the reaction times is 1h～4h.
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| CN201210325806.9A CN103664634B (en) | 2012-09-06 | 2012-09-06 | For loaded catalyst prepared by 1,2 propane diamine |
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|---|---|---|---|
| CN201210325806.9A CN103664634B (en) | 2012-09-06 | 2012-09-06 | For loaded catalyst prepared by 1,2 propane diamine |
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| CN103664634A true CN103664634A (en) | 2014-03-26 |
| CN103664634B CN103664634B (en) | 2017-06-16 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108704644A (en) * | 2018-06-13 | 2018-10-26 | 苏州大学 | The meso-porous alumina tiny balloon of load nano cupric oxide and its preparation and application |
| CN112121812A (en) * | 2020-09-16 | 2020-12-25 | 万华化学集团股份有限公司 | Catalyst for preparing propane diamine, preparation method of catalyst and method for preparing propane diamine |
| CN113105336A (en) * | 2021-04-15 | 2021-07-13 | 山东达民化工股份有限公司 | Preparation method of 1, 2-propane diamine |
| CN114105812A (en) * | 2020-08-26 | 2022-03-01 | 中国石油化工股份有限公司 | Method for synthesizing N, N' -bis (salicylidene) -1, 2-propane diamine by using chloropropene byproduct 1, 2-dichloropropane |
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| PL209534B1 (en) * | 2006-07-11 | 2011-09-30 | Univ West Pomeranian Szczecin Tech | Method for the obtaining 1, 2-diaminopropane and polypropyleneamines |
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2012
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Patent Citations (4)
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| US2078555A (en) * | 1934-04-30 | 1937-04-27 | Barbierl Cesare | Production of amines by emulsion method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108704644A (en) * | 2018-06-13 | 2018-10-26 | 苏州大学 | The meso-porous alumina tiny balloon of load nano cupric oxide and its preparation and application |
| CN108704644B (en) * | 2018-06-13 | 2020-07-07 | 苏州大学 | Mesoporous alumina hollow microsphere loaded with nano copper oxide and preparation and application thereof |
| CN114105812A (en) * | 2020-08-26 | 2022-03-01 | 中国石油化工股份有限公司 | Method for synthesizing N, N' -bis (salicylidene) -1, 2-propane diamine by using chloropropene byproduct 1, 2-dichloropropane |
| CN112121812A (en) * | 2020-09-16 | 2020-12-25 | 万华化学集团股份有限公司 | Catalyst for preparing propane diamine, preparation method of catalyst and method for preparing propane diamine |
| CN113105336A (en) * | 2021-04-15 | 2021-07-13 | 山东达民化工股份有限公司 | Preparation method of 1, 2-propane diamine |
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