阅读说明：本技术 一种制备高纯度聚合级间苯二胺的方法 (A method of preparing high-purity polymer grade m-phenylene diamine (MPD) ) 是由 杜成平 向勇 冯刚 张建琴 黄清武 蒲祖伦 于 2019-09-17 设计创作，主要内容包括：本发明提供了一种制备高纯度聚合级间苯二胺的方法,以混合二硝基苯为原料,加入醇溶剂、催化剂,进行催化加氢生成混合二氨基苯还原液,再经过脱醇、脱水、脱焦、精馏得到灰品间苯二胺；灰品间苯二胺经过结晶、蒸馏处理得到聚合级间苯二胺成品,本发明不产生三废,更绿色经济环保,间苯二胺产品的纯度更高,不含有对苯二胺及邻苯二胺类其他杂质。(The present invention provides a kind of methods for preparing high-purity polymer grade m-phenylene diamine (MPD), to mix dinitrobenzene as raw material, alcoholic solvent, catalyst is added, carries out catalytic hydrogenation and generates mixing diaminobenzene reducing solution, obtain grey product m-phenylene diamine (MPD) using dealcoholysis, dehydration, decoking, rectifying；Grey product m-phenylene diamine (MPD) handles to obtain polymer grade m-phenylene diamine (MPD) finished product by crystallization, distillation, and the present invention does not generate the three wastes, and the environmental protection of more green economy, the purity of m-phenylene diamine (MPD) product is higher, does not contain p-phenylenediamine and o-phenylenediamine class other impurities.)

1. a kind of method for preparing high-purity polymer grade m-phenylene diamine (MPD), which comprises the following steps:

(1) to mix dinitrobenzene as raw material, alcoholic solvent, catalyst is added, carries out catalytic hydrogenation and generates mixing diaminobenzene also Stoste；

(2) the mixing diaminobenzene reducing solution prepared in step (1) is obtained into grey product isophthalic by dealcoholysis, dehydration, decoking, rectifying Diamines；

(3) crystallizer, crystallizer temperature are sent into after mixing the grey product m-phenylene diamine (MPD) in step (2) by the mass ratio of 1:2~3 with water Degree maintains 40~80 DEG C, and crystallizer is cooled to 15~25 DEG C after 5~8h and is crystallized, mother liquor is released after crystallization；

(4) m-phenylenediamine solution is melted into obtain in the crystal heating after crystallization in step (3), m-phenylenediamine solution is sent into distillation still Interior carry out vacuumize process makes to be dehydrated under the pressure for maintaining 1-10kPa in distillation still, distill, obtains polymer grade isophthalic Diamines finished product；

(5) the m-phenylene diamine (MPD) finished product produced in step (4) is subjected under the conditions of inert atmosphere protection film-making packaging, obtained high-purity M-phenylene diamine (MPD) finished product.

2. the method for preparation high-purity polymer grade m-phenylene diamine (MPD) according to claim 1, which is characterized in that in step (3) The mother liquor of releasing recycles grey product m-phenylene diamine (MPD) after dehydration.

3. the method for preparation high-purity polymer grade m-phenylene diamine (MPD) according to claim 1, which is characterized in that in step (3) First mould temperature is controlled at 70~80 DEG C, is cooled down using recirculated water, after 2~4h of temperature fall time, then crystallizer is dropped Then temperature bleeds off recirculated water to 40~50 DEG C, using 2~8 DEG C of chilled water, after maintaining 3~4h, then crystallizer is cooled down and is tied It is brilliant.

4. the method for preparation high-purity polymer grade m-phenylene diamine (MPD) according to claim 1, which is characterized in that in step (4) Melt crystal using steam, control melt temperature is 60~90 DEG C.

5. the method for preparation high-purity polymer grade m-phenylene diamine (MPD) according to claim 1, which is characterized in that in step (1) The alcoholic solvent quality is mix dinitrobenzene material quality 30%~40%, and the catalyst quality is mixing dinitrobenzene The 1.5-3% of material quality.

6. the method for preparation high-purity polymer grade m-phenylene diamine (MPD) according to claim 1, which is characterized in that in step (1) The alcoholic solvent is the alcohol of C1~C4.

7. the method for preparation high-purity polymer grade m-phenylene diamine (MPD) according to claim 1, which is characterized in that in step (1) The catalyst is Raney nickel, palladium catalyst or platinum catalyst.

8. the method for preparation high-purity polymer grade m-phenylene diamine (MPD) according to claim 1, which is characterized in that in step (1), The reaction condition of catalytic hydrogenation are as follows: Hydrogen Vapor Pressure is controlled in 1.5~2.0MPa, temperature at 100~130 DEG C.

9. the method for preparation high-purity polymer grade m-phenylene diamine (MPD) according to claim 1, which is characterized in that in step (2), Heating distillation removing alcoholic solvent and water under normal pressure, then carry out distillation decoking under 3000pa vacuum, the material warp after decoking It crosses rectifying under vacuum and separates ash output yield m-phenylene diamine (MPD), while generating grey product o-phenylenediamine and grey product p-phenylenediamine.

10. the method for preparation high-purity polymer grade m-phenylene diamine (MPD) according to claim 1, which is characterized in that step (5) In, the inert atmosphere is the one or more of high-purity nitrogen, helium or argon gas.

Technical field

The invention belongs to m-phenylene diamine (MPD) production technical fields, specifically, being related to a kind of preparing high-purity polymer grade isophthalic The method of diamines.

Background technique

M-phenylene diamine (MPD) is a kind of important dyestuff intermediate, can be used for synthesizing all kinds of basic dyes, while it or one The important fragrant limb class curing agent of kind, is widely used in composite material and plastic applications.It is prepared by traditional m-phenylene diamine (MPD) production Using benzene as raw material, mixing dinitrobenzene is obtained by nitrification, mixing dinitrobenzene is refining to obtain two between high-purity through sodium sulfite Nitrobenzene, m-dinitrobenzene with methanol (or ethyl alcohol) for solvent, in the presence of a nickel catalyst plus hydrogen, crystallization, rectifying obtain it is high-purity Spend polymer grade m-phenylene diamine (MPD) product.

It is low that traditional m-phenylene diamine (MPD) prepares yield, and preparation process generates a large amount of waste water, is conducive to industrialized production and environmental protection warp Ji.

Summary of the invention

For deficiency above-mentioned in the prior art, high-purity polymer grade isophthalic is prepared the purpose of the present invention is to provide a kind of The method of diamines, using this method, the utilization rate that raw material can be improved, reduces wastewater treatment difficulty, drop at the yield for reducing the three wastes The production cost of oligomerization grade m-phenylene diamine (MPD) improves product competitiveness in the market.

In order to achieve the above object, the solution that the present invention uses is:

A method of preparing high-purity polymer grade m-phenylene diamine (MPD), comprising the following steps:

(1) to mix dinitrobenzene as raw material, alcoholic solvent, catalyst is added, carries out catalytic hydrogenation and generates mixing diamino Benzene reducing solution；

(2) the mixing diaminobenzene reducing solution prepared in step (1) is obtained into grey product by dealcoholysis, dehydration, decoking, rectifying M-phenylene diamine (MPD)；

(3) the grey product m-phenylene diamine (MPD) in step (2) is melted in advance and is sent into after being mixed with water by the mass ratio of 1:2~3 Crystallizer, mould temperature maintain 40~80 DEG C, and crystallizer is cooled to 15~25 DEG C after 5~8h and is crystallized, crystallization knot Mother liquor is released after beam；

(4) m-phenylenediamine solution is melted into obtain in the crystal heating after crystallization in step (3), m-phenylenediamine solution is sent into and is steamed It evaporates and carries out vacuumize process in kettle, make to be dehydrated under the pressure for maintaining 1-10kPa in distillation still, distill, obtain polymer grade M-phenylene diamine (MPD) finished product；

(5) the m-phenylene diamine (MPD) finished product produced in step (4) is subjected under the conditions of inert atmosphere protection film-making packaging, obtained High-purity m-phenylene diamine (MPD) finished product.

Further, the mother liquor released in step (3) recycles grey product m-phenylene diamine (MPD) after dehydration.

Further, first mould temperature is controlled at 70~80 DEG C in step (3), is cooled down using recirculated water, dropped After warm 2~4h of time, then crystallizer is cooled to 40~50 DEG C, then bleeds off recirculated water, use 2~8 DEG C of chilled water, maintained After 3~4h, then by crystallizer decrease temperature crystalline.

Further, melt crystal using steam in step (4), control melt temperature is 60~90 DEG C.

Further, alcoholic solvent quality described in step (1) is mix dinitrobenzene material quality 30%~40%, institute Stating catalyst quality is the 1.5-3% for mixing dinitrobenzene material quality.

Further, alcoholic solvent described in step (1) is the alcohol of C1~C4, preferably methanol.

Further, catalyst described in step (1) is Raney nickel, palladium catalyst or platinum catalyst.

Further, in step (1), the reaction condition of catalytic hydrogenation are as follows: Hydrogen Vapor Pressure is in 1.5~2.0MPa, temperature control System is at 100~130 DEG C.

Further, in step (2), heating distillation under normal pressure removes alcoholic solvent and water, then under 3000pa vacuum Distillation decoking is carried out, the material after decoking passes through rectifying under vacuum and separates ash output yield m-phenylene diamine (MPD), while generating grey product neighbour benzene two Amine and grey product p-phenylenediamine.

Further, the inert atmosphere is the one or more of high-purity nitrogen, helium or argon gas.

The beneficial effects of the present invention are:

1. inventor has found: during mixing dinitrobenzene is refining to obtain high puremdinitrobenzene through sodium sulfite, Generation will be reacted with sodium sulfite and is dissolved in the two of water by accounting for about 15% o-dinitrobenzene and paradinitrobenzene in mixing dinitrobenzene Nitrobenzene sodium sulfonate causes the maximum yield of m-dinitrobenzene there was only 85%, and then influences the receipts of final m-phenylene diamine (MPD) product Rate, and the waste water for being largely difficult to the sodium containing dinitrobenzene sulfonic acid handled is generated during sodium sulfite refines, it is unfavorable for work Industry metaplasia produces and environmental protection and economy；Compared with prior art, the present invention using separating technology after mixing hydrogenation of dinitro toluene than existing Have using sodium sulfite process for refining it is more economical more environmentally friendly, can will mix dinitrobenzene in account for about 15% dinitrobenzene isomer By isolating p-phenylenediamine, o-phenylenediamine product after adding hydrogen, then removed by redistilled mode after crystallization, between improving The purity and yield of phenylenediamine, while reaching the requirement of polymer grade.

2. present invention process, which avoids, contains a large amount of dinitrobenzene sulfonic acid sodium by what dinitrobenzene purification generated in the prior art Waste water, the environmental protection of present invention process more green economy.

3. water is only added in present invention process crystallization process, grey product isophthalic is recycled in the mother liquor Direct Dehydration processing for crystallizing generation Diamines, it is on the one hand more shorter than prior art mother liquor dealcoholation treatment process flow, it handles more simple and environmentally-friendly；On the other hand pass through by Recycling ash product m-phenylene diamine (MPD) after mother liquor by dewatering processing, improves the yield of m-phenylene diamine (MPD) finished product.

Specific embodiment

It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase Product.

Below to it is provided in an embodiment of the present invention it is a kind of prepare high-purity polymer grade m-phenylene diamine (MPD) method carry out specifically It is bright.

A method of preparing high-purity polymer grade m-phenylene diamine (MPD), comprising the following steps:

(1) to mix dinitrobenzene as raw material, alcoholic solvent, catalyst is added, carries out catalytic hydrogenation and generates mixing diamino Benzene reducing solution；Mixing dinitrobenzene is passed through into catalytic hydroconversion as mixing diaminobenzene, the separating technology is more than prior art It is economical more environmentally friendly, and the technique can will mix the dinitrobenzene isomer for accounting for about 15% in dinitrobenzene by separating life after adding hydrogen At p-phenylenediamine, o-phenylenediamine product, avoids and contain a large amount of dinitrobenzene sulphurs by what dinitrobenzene purification generated in the prior art The waste water of sour sodium, the more economical environmental protection of present invention process；

(2) the mixing diaminobenzene reducing solution prepared in step (1) is obtained into grey product by dealcoholysis, dehydration, decoking, rectifying M-phenylene diamine (MPD)；

(3) it is sent into crystallizer after mixing the grey product m-phenylene diamine (MPD) in step (2) by the mass ratio of 1:2~3 with water, is crystallized Device temperature maintains 40~80 DEG C, and crystallizer is cooled to 15~25 DEG C after 5~8h and is crystallized, and releases after crystallization female Liquid；Grey product m-phenylene diamine (MPD) obtains the m-phenylene diamine (MPD) crystal of higher degree by crystallization processes, in the process can will be between grey product Toluenediamine class impurity removal in phenylenediamine.

(4) m-phenylenediamine solution is melted into obtain in the crystal heating after crystallization in step (3), m-phenylenediamine solution is sent into and is steamed It evaporates and carries out vacuumize process in kettle, make to be dehydrated under the pressure for maintaining 1-10kPa in distillation still, distill, obtain polymer grade M-phenylene diamine (MPD) finished product；O-phenylenediamine and p-phenylenediamine class impurity in m-phenylene diamine (MPD) are removed by redistilled mode after crystallization, The purity and yield of m-phenylene diamine (MPD) are improved, while reaching the requirement of polymer grade.

(5) the m-phenylene diamine (MPD) finished product produced in step (4) is subjected under the conditions of inert atmosphere protection film-making packaging, obtained M-Phenylenediamine of High Purity finished product.It prevents finished product and air contact metamorphism and influences the quality of finished product.

Further, the mother liquor released in step (3) recycles grey product m-phenylene diamine (MPD) after dehydration.Because in crystallization process Water is only added, other organic solvents are not added, the mother liquor for crystallizing generation directly returns to i.e. recyclable ash after dehydrating tower dehydration Organic solvent is added in product m-phenylene diamine (MPD), one side prior art crystallization process, and the mother liquor of generation needs at alcohol tower progress dealcoholysis back off Reason, this technique dehydration technique are short compared to dealcoholation treatment process flow, and processing is simple more environmentally friendly；On the other hand by by mother liquor Recycling ash product m-phenylene diamine (MPD) after dehydration, improves the yield of product.

Further, first mould temperature is controlled at 70~80 DEG C in step (3), is cooled down using recirculated water, dropped After warm 2~4h of time, then crystallizer is cooled to 40~50 DEG C, then bleeds off recirculated water, use 2~8 DEG C of chilled water, maintained After 3~4h, then by crystallizer decrease temperature crystalline.

Further, melt crystal using steam in step (4), control melt temperature is 60~90 DEG C.

Further, alcoholic solvent quality described in step (1) is mix dinitrobenzene material quality 30%~40%, institute Stating catalyst quality is the 1.5-3% for mixing dinitrobenzene material quality.

Further, alcoholic solvent described in step (1) is the alcohol of C1~C4, such as methanol, ethyl alcohol, but more preferably uses first Alcohol is as solvent, and because the dissolution of methanol paradinitrobenzene is more preferable, more conducively hydrogenation reaction, reduction tar are generated.

Further, catalyst described in step (1) is Raney nickel, such as: skeleton nickel, carrier nickel, reduced nickel and boronation Nickel；Palladium catalyst, such as: palladium carbon, palladium oxide, palladium black and carrier palladium；Or platinum catalyst, such as: platinum oxide, platinum black and carrier platinum.It is logical Addition Raney nickel, palladium catalyst or platinum catalyst are crossed, is conducive to the efficient progress of catalytic hydrogenation reaction, in the present embodiment preferably Using skeleton nickel, that is, Raney's nickel, so that present invention process is more economical.

Further, in step (1), the reaction condition of catalytic hydrogenation are as follows: Hydrogen Vapor Pressure is in 1.5~2.0MPa, temperature control System is at 100~130 DEG C.

Further, in step (2), heating distillation under normal pressure removes alcoholic solvent and water, then under 3000pa vacuum Distillation decoking is carried out, the material after decoking passes through rectifying under vacuum and separates ash output yield m-phenylene diamine (MPD), while generating grey product neighbour benzene two Amine and grey product p-phenylenediamine.

Further, in step (5), the inert atmosphere is the one or more of high-purity nitrogen, helium or argon gas, this Nitrogen is preferably used in inventive embodiments.