CN104326920A - Method for removing impurities in 1,3-bis(aminomethyl)benzene - Google Patents
Method for removing impurities in 1,3-bis(aminomethyl)benzene Download PDFInfo
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- CN104326920A CN104326920A CN201410537652.9A CN201410537652A CN104326920A CN 104326920 A CN104326920 A CN 104326920A CN 201410537652 A CN201410537652 A CN 201410537652A CN 104326920 A CN104326920 A CN 104326920A
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Abstract
The invention discloses a method for removing impurities in 1,3-bis(aminomethyl)benzene. The method comprises contacting a catalyst with impurity-containing 1,3-bis(aminomethyl)benzene in an organic solvent in the presence of hydrogen and ammonia gas. The method is simple to operate, and is capable of effectively reducing impurities in 1,3-bis(aminomethyl)benzene without adding extra investment.
Description
Technical field
The present invention relates to one and go deimpurity method, particularly, relate to a kind of method removing impurity in m-xylene diamine.
Background technology
M-xylene diamine (MXDA), as a kind of aromatics aminate, chemical industry has and applies very widely.M-xylene diamine is mainly used as epoxy curing agent, also can be used for making fine chemical material.In solidifying agent, oneself accounts for a greater part of of its aggregate consumption in current Japan, in this ratio of China also up to 80%; MXDA is through photochmeical reaction synthesis m-xylene two isocyanate, and then synthesis polyurethane, mainly for the production of the polyurethane resin paint of resistance to flavescence.The production of China MXDA solidifying agent and application are still in the starting stage, and according to breed structure and the development trend of state's coated sand intensifier, the consumption potentiality in MXDA and modification MXDA solidifying agent epoxy resin field are at home very large, wide market.Gas chemical company of Mitsubishi to go into operation MXDA in nineteen eighty-two, and yearly capacity is at that time 4000 tons, is progressively extended to 20,000 tons afterwards, and within 2000, device capability expands to 30,000 tons, and present aggregated capacity has been extended to 60,000 tons.The China's starting seventies, although there has been the course of 40 years till now, but also have no small gap with Mitsubishi gas, be mainly manifested in international market share little, quality product is not high.How to produce high-quality MXDA, reduce foreign matter content, become a common difficult problem in the industry.As everyone knows, easily produce a small amount of oxidation impurities in the production process of amine curing agent, these impurity have a strong impact on the quality of MXDA.To mainly contain two: one be the micro amount of oxygen compound that raw band is come in its source, is on the other hand to react with a small amount of moisture in reaction solution in MXDA deamination process to be formed.The main way of industry by follow-up rectifying, these magazins' layout is gone out, but will to be reduced to less than 0.1% be very difficult, not only needs the investment of at substantial rectifying device, also can reduce output, cause high expensive.
Summary of the invention
The object of the invention is the method complicated operation overcoming impurity in existing removing m-xylene diamine, the high and defect yielded poorly of cost of investment, and the method for impurity in a kind of removal m-xylene diamine is newly provided.
To achieve these goals, the invention provides a kind of method removing impurity in m-xylene diamine, the method comprises: under hydrogen and ammonia exist, catalyzer is contacted in organic solvent with impure m-xylene diamine, wherein, described impurity is the compound shown in formula (1)
Method of the present invention is simple to operate, the impurity in m-xylene diamine can be effectively reduced while additionally not increasing investment, in a preferred embodiment of the invention, the amination reaction of effective inhibition of impurities can carry out to reverse direction, finally can reduce below foreign matter content to 0.1%.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of method removing impurity in m-xylene diamine, the method comprises: under hydrogen and ammonia exist, contacted in organic solvent by catalyzer, wherein with impure m-xylene diamine, described impurity is the compound shown in formula (1)
According to the present invention, in described impure m-xylene diamine, the content of impurity is preferably 0.01-10 quality %, more preferably 0.05-5 quality %.
According to the present invention, described impure m-xylene diamine is under hydrogen and ammonia exist, and concrete reaction is as shown in following formula (a):
formula (a),
Wherein, as long as described catalyzer is by the conversion of hydroxyl in reactant for amino, that is, under the catalysis of described catalyzer, reactant (impurity) can be converted into m-xylene diamine (product).In embodiments of the invention, described catalyzer is preferably Raney Ni (Raney Ni).
According to the present invention, described Raney Ni can be purchased also can be made by oneself.Raney Ni in the present invention adopts self-control, and the preparation method that homemade method is known to the skilled person, specifically comprises following step:
(1) sodium hydroxide is thrown into be equipped with in the there-necked flask of purified water, the flask that sodium hydroxide solution is housed is being placed in ice-water bath;
(2) stirring is opened, within a certain period of time al-ni alloy powder is slowly joined in above-mentioned sodium hydroxide solution, because al-ni alloy powder can release a large amount of hydrogen and heat with aqueous sodium hydroxide solution vigorous reaction, now need the speed controlling to add, guarantee that the temperature of reaction in flask is no more than 50 DEG C, after adding, be warmed up to 90 DEG C and continue insulation reaction;
(3) after having reacted, cool to 40 DEG C, the Raney Ni in flask is poured in beaker together with the aqueous solution, then leave standstill for some time, pour out the aqueous solution above;
(4) add in above-mentioned beaker again deionized water carry out washing, stir, leave standstill, pour out above the aqueous solution;
(5) repeating step (4) 4-7 time, until the pH value of the aqueous solution poured out is between 8-9;
(6) after having washed, then add methyl alcohol in beaker, stir, leave standstill, pour out methanol solution above;
(7) repeating step (6) 3 times, is finally kept at above-mentioned Raney Ni in methyl alcohol, completes the preparation of Raney Ni.
According to the present invention, be all converted into product and m-xylene diamine to make impurity not be converted into other impurity, the contact of described catalyzer and impure m-xylene diamine is preferably carried out under basic cpd exists.
According to the present invention, in order to make impurity be converted into product and m-xylene diamine fully, the mass ratio of described basic cpd and described impure m-xylene diamine is preferably 0.001-0.01:1, is more preferably 0.005-0.009:1.
According to the present invention, the basic cpd that described basic cpd can be known to the skilled person.Such as, basic cpd can be one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate.Sodium hydroxide is preferably in embodiments of the invention.
According to the present invention, be all converted into product and m-xylene diamine to make impurity not be converted into other impurity, described organic solvent be preferably in alcoholic solvent and benzene kind solvent one or more; One or more more preferably in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, toluene, o-Xylol, m-xylene, p-Xylol, isopropyl benzene and n-proplbenzene; Be more preferably methyl alcohol and/or toluene.
According to the present invention, in order to make impurity be converted into product and m-xylene diamine fully, the volume ratio of described alcoholic solvent and described benzene kind solvent is preferably 1-5:1, more preferably 3:1.
According to the present invention, in order to make impurity be converted into product and m-xylene diamine fully, the mass ratio of described catalyzer and described impure m-xylene diamine is preferably 0.1-0.5:1, more preferably 0.25-0.35:1.
According to the present invention, in order to make impurity be converted into product and m-xylene diamine fully, the mass ratio of described impure m-xylene diamine and described ammonia is preferably 0.1-100:1, more preferably 1-55:1.
The present invention does not have special requirement to described ammonia, as long as be amino by the conversion of hydroxyl in impurity.
According to the present invention, be all converted into product and m-xylene diamine to make impurity not be converted into other impurity, the condition of described contact comprises: temperature is preferably 120-250 DEG C, more preferably 150-200 DEG C; Pressure is preferably 5-15MPa, more preferably 10-13MPa.
In the present invention, the reaction of formula (a) can be carried out in any high-pressure reactor, such as, and autoclave etc.
In the present invention, the reaction times of formula (a) is preferably 10-100min, more preferably 40-80min; After reaction terminates, preferably, the temperature of reaction is down to less than 35 DEG C, and Pressure Drop is to normal pressure.
According to one of the present invention preferred embodiment, first in autoclave, add the m-xylene diamine containing impurity, the mixing solutions (alcoholic solvent: benzene kind solvent=1-5:1) of alcoholic solvent and benzene kind solvent, basic cpd and raney nickel catalyst; Build kettle cover, with the air in nitrogen replacement still, pressure release to normal pressure, then uses the nitrogen in hydrogen exchange still, lets out to normal pressure; Be filled with ammonia, then pass into hydrogen, react at a temperature and pressure as described above, after terminating, be cooled to normal temperature, be depressurized to normal pressure, extract reaction solution the residual volume by gas chromatographic analysis checked for impurities.
Below will be described the present invention by embodiment.In following examples, the residual volume of impurity is recorded by gas chromatograph, and gas chromatograph is that Agilent company produces, and model is GC7890.
If no special instructions, in the present invention, percentage composition all refers to mass percentage.
Preparation example
Being thrown into by 237g sodium hydroxide is equipped with in the 2L there-necked flask of 1086g purified water, and the flask that sodium hydroxide solution is housed is being placed in ice-water bath; Open stirring, by 200g al-ni alloy powder in 1.5h, slowly join in above-mentioned sodium hydroxide solution, because al-ni alloy powder can release a large amount of hydrogen and heat with aqueous sodium hydroxide solution vigorous reaction, now need the speed controlling to add, guarantee that the temperature of reaction in flask is no more than 50 DEG C, after adding, be warmed up to 90 DEG C and continue insulation reaction 2h; After having reacted, cool to 40 DEG C, the Raney Ni in flask is poured in the beaker of 2L together with the aqueous solution, then leave standstill 10min, pour out the aqueous solution above; In above-mentioned beaker, add 800mL deionized water again to wash, stir 0.5h, leave standstill 10min, pour out the aqueous solution above; Wash 4-7 time according to above-mentioned method for washing, until the pH value of the aqueous solution poured out is between 8-9; After having washed, then add 800mL methyl alcohol in beaker, stir 0.5h, leave standstill 10min, pour out methanol solution above; Wash 3 times according to above-mentioned alcohol washing method, obtain raney nickel catalyst, raney nickel catalyst is kept in 500mL methyl alcohol.
Embodiment 1
The m-xylene diamine that 106g foreign matter content is 0.05 % by weight is added successively in the autoclave of 1L, the mixing solutions (methyl alcohol: toluene=3:1) of 400mL methyl alcohol and toluene, raney nickel catalyst prepared by 0.7g sodium hydroxide and the above-mentioned preparation example of 30g; Build kettle cover, with the air in nitrogen replacement still three times, pressure release to normal pressure, then uses nitrogen in hydrogen exchange still three times, lets out to normal pressure; Be filled with 2.5g ammonia, then pass into hydrogen, react at temperature 180 DEG C and pressure 12MPa; After reaction 60min, be cooled to 30 DEG C, be depressurized to normal pressure.Extracting reaction solution with the residual volume of gas chromatographic analysis checked for impurities is 0%.
Embodiment 2
The m-xylene diamine that 110g foreign matter content is 1 % by weight is added successively in the autoclave of 1L, the mixing solutions (methyl alcohol: toluene=3:1) of 800mL methyl alcohol and toluene, raney nickel catalyst prepared by 0.55g sodium hydroxide and the above-mentioned preparation example of 33g; Build kettle cover, with the air in nitrogen replacement still three times, pressure release to normal pressure, then uses nitrogen in hydrogen exchange still three times, lets out to normal pressure; Be filled with 2g ammonia, then pass into hydrogen, react at temperature 200 DEG C and pressure 10MPa; After reaction 60min, be cooled to 25 DEG C, be depressurized to normal pressure.Extracting reaction solution with the residual volume of gas chromatographic analysis checked for impurities is 0.01%.
Embodiment 3
The m-xylene diamine that 114g foreign matter content is 3 % by weight is added successively in the autoclave of 1L, the mixing solutions (methyl alcohol: toluene=3:1) of 800mL methyl alcohol and toluene, raney nickel catalyst prepared by 1.03g sodium hydroxide and the above-mentioned preparation example of 40g; Build kettle cover, with the air in nitrogen replacement still three times, pressure release to normal pressure, then uses nitrogen in hydrogen exchange still three times, lets out to normal pressure; Be filled with 114g ammonia, then pass into hydrogen, react at temperature 150 DEG C and pressure 13MPa; After reaction 60min, be cooled to 30 DEG C, be depressurized to normal pressure.Extracting reaction solution with the residual volume of gas chromatographic analysis checked for impurities is 0.08%.
Embodiment 4
The m-xylene diamine that 120g foreign matter content is 5 % by weight is added successively, the mixing solutions (methyl alcohol: toluene=1:1) of 800mL methyl alcohol and toluene, raney nickel catalyst prepared by 1.2g potassium hydroxide and the above-mentioned preparation example of 12g in the autoclave of 1L; Build kettle cover, with the air in nitrogen replacement still three times, pressure release to normal pressure, then uses nitrogen in hydrogen exchange still three times, lets out to normal pressure; Be filled with 1.2g ammonia, then pass into hydrogen, react at temperature 120 DEG C and pressure 15MPa; After reaction 40min, be cooled to 25 DEG C, be depressurized to normal pressure.Extracting reaction solution with the residual volume of gas chromatographic analysis checked for impurities is 0.15%.
Embodiment 5
The m-xylene diamine that 120g foreign matter content is 8 % by weight is added successively in the autoclave of 1L, the mixing solutions (ethanol: p-Xylol=5:1) of 1000mL ethanol and p-Xylol, raney nickel catalyst prepared by 0.12g sodium bicarbonate and the above-mentioned preparation example of 60g; Build kettle cover, with the air in nitrogen replacement still three times, pressure release to normal pressure, then uses nitrogen in hydrogen exchange still three times, lets out to normal pressure; Be filled with 2g ammonia, then pass into hydrogen, react at temperature 250 DEG C and pressure 5MPa; After reaction 80min, be cooled to 25 DEG C, be depressurized to normal pressure.Extracting reaction solution with the residual volume of gas chromatographic analysis checked for impurities is 0.19%.
Embodiment 6
The impurity in m-xylene diamine is removed according to the method for embodiment 1, unlike, the mixing solutions of methyl alcohol and toluene is replaced with methyl alcohol.Extracting reaction solution with the residual volume of gas chromatographic analysis checked for impurities is 0.39%.
Embodiment 7
The impurity in m-xylene diamine is removed according to the method for embodiment 2, unlike, Raney Ni is replaced with loading type Ni/Al
2o
3(Ni content is 10%).Extracting reaction solution with the residual volume of gas chromatographic analysis checked for impurities is 0.58%.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. remove a method for impurity in m-xylene diamine, the method comprises: under hydrogen and ammonia exist, contacted in organic solvent with impure m-xylene diamine by catalyzer, wherein, described impurity is the compound shown in formula (1),
2. method according to claim 1, wherein, described contact is carried out under basic cpd exists.
3. method according to claim 1, wherein, the mass ratio of described basic cpd and described impure m-xylene diamine is 0.001-0.01:1, is preferably 0.005-0.009:1.
4. method according to claim 1, wherein, described basic cpd is one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate, is preferably sodium hydroxide.
5. method according to claim 1, wherein, described catalyzer is Raney Ni.
6. method according to claim 1, wherein, described organic solvent is one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, toluene, o-Xylol, m-xylene, p-Xylol, isopropyl benzene and n-proplbenzene.
7. method according to claim 1 or 5, wherein, the mass ratio of described catalyzer and described impure m-xylene diamine is 0.1-0.5:1, is preferably 0.25-0.35:1.
8. method according to claim 1, wherein, the mass ratio of described impure m-xylene diamine and described ammonia is 0.1-100:1.
9. method according to claim 8, wherein, the mass ratio of described impure m-xylene diamine and described ammonia is 1-55:1.
10. method according to claim 1 and 2, wherein, the condition of described contact comprises: temperature is 120-250 DEG C, is preferably 150-200 DEG C; Pressure is 5-15MPa, is preferably 10-13MPa.
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| US20060094904A1 (en) * | 2004-10-28 | 2006-05-04 | Sundaram Venkataraman | Process for preparing tolterodine |
| CN103228612A (en) * | 2010-12-08 | 2013-07-31 | 赢创德固赛有限公司 | Process for homogeneously catalyzed, highly selective direct amination of primary alcohols with ammonia to primary amines with a high volume ratio of liquid phase to gas phase and/or high pressures |
| CN103370302A (en) * | 2011-02-21 | 2013-10-23 | 赢创德固赛有限公司 | Process for the direct amination of alcohols using ammonia to form primary amines by means of a Xantphos catalyst system |
| US20130303741A1 (en) * | 2008-06-02 | 2013-11-14 | Generics [Uk] Limited | Process for the preparation of enantiomerically pure amines |
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2014
- 2014-10-13 CN CN201410537652.9A patent/CN104326920B/en active Active
Patent Citations (4)
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| US20060094904A1 (en) * | 2004-10-28 | 2006-05-04 | Sundaram Venkataraman | Process for preparing tolterodine |
| US20130303741A1 (en) * | 2008-06-02 | 2013-11-14 | Generics [Uk] Limited | Process for the preparation of enantiomerically pure amines |
| CN103228612A (en) * | 2010-12-08 | 2013-07-31 | 赢创德固赛有限公司 | Process for homogeneously catalyzed, highly selective direct amination of primary alcohols with ammonia to primary amines with a high volume ratio of liquid phase to gas phase and/or high pressures |
| CN103370302A (en) * | 2011-02-21 | 2013-10-23 | 赢创德固赛有限公司 | Process for the direct amination of alcohols using ammonia to form primary amines by means of a Xantphos catalyst system |
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| MATTHIAS BELLER等: "Improved Ruthenium-Catalyzed Amination of Alcohols with Ammonia: Synthesis of Diamines and Amino Esters", 《ANGEW. CHEM. INT. ED.》 * |
| 吕自红等: "改性雷尼镍在合成间苯二甲胺反应中的性能研究", 《浙江化工》 * |
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