CN107540556B - Preparation method of m-xylylenediamine - Google Patents
Preparation method of m-xylylenediamine Download PDFInfo
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Abstract
A method for producing m-xylylenediamine is characterized in that: pumping an isophthalonitrile solution dissolved in a mixed solvent into a bed layer filled with a Ni/MgAlO catalyst by adopting a fixed bed reactor, wherein the temperature is 60-140 ℃, the pressure is 1.0-8.0 MPa, and the mass space velocity of isophthalonitrile is 0.1-5 h‑1And reacting the isophthalonitrile with hydrogen to generate m-xylylenediamine under the condition that the molar ratio of the hydrogen to the isophthalonitrile is 5-50: 1. Under the optimized reaction condition, the yield of m-xylylenediamine can reach 100 percent at most, and the method can be suitable for industrial continuous production.
Description
Technical Field
The invention relates to a preparation method of m-xylylenediamine, belonging to the technical field of catalytic hydrogenation.
Technical Field
The m-xylylenediamine (MXDA) is an epoxy resin curing agent with excellent performance, has the advantages of low-temperature curing, heat resistance, water resistance, good chemical corrosion resistance, low viscosity, easiness in operation and the like, can be applied to the fields of polyurethane, polyamide, rubber additives, pesticides, fiber finishing agents, rust removers, chelating agents, lubricants, paper processing aids, electronic chemicals and the like, and is a fine chemical with wide application and high added value.
M-xylylenediamine is generally produced by a catalytic hydrogenation process of m-phthalonitrile. The domestic industrial production of m-xylylenediamine is mainly carried out by batch still kettle type reaction, the production scale is small, the catalyst particles are fine, the pulverization is easy, the separation effect is poor, the production cost is higher, the safety is poor, the automation degree is low and the like. While the major international manufacturers, such as Mitsubishi gas in Japan, use the trickle bed continuous process, the German Pasteur also uses the fixed bed catalytic process. The intermittent reaction mainly adopts Raney nickel or modified Raney nickel, and the fixed bed process mostly adopts a supported nickel-based catalyst.
An imine intermediate with high reaction activity is generated in the intermediate process of the isophthalonitrile hydrogenation reaction, and the imine intermediate is easy to further perform polycondensation reaction with an intermediate product and a target product of the reaction to generate secondary amine, tertiary amine and other high-boiling-point polymerization byproducts, and the byproducts are adsorbed and deposited on the surface of the catalyst to cause the poisoning and inactivation of the catalyst. An important method for suppressing the polycondensation side reaction is to use an excess of liquid ammonia or ammonia gas or an organic amine as an inhibitor. For example, CN101774928 discloses a method for preparing m-xylylenediamine, which comprises dissolving m-phthalonitrile in an amide solvent, and performing hydrogenation reaction on a supported Co — Ni catalyst by using liquid ammonia as a byproduct inhibitor, wherein the yield of m-xylylenediamine reaches 99.96%. But the recovery cost of using a large amount of liquid ammonia is high, and a large amount of ammonia-containing waste gas and waste water are generated, so that the pollution is serious. CN101955432 discloses a method for preparing m-xylylenediamine by batch hydrogenation in a stirred tank, which adopts a modified raney nickel catalyst, and uses a ternary mixed solvent of aromatic hydrocarbon, low carbon alcohol and aliphatic halogenated derivatives and secondary amine inhibitors such as triethylamine, diethylamine and the like in the reaction. CN102690205 discloses a process for preparing m-xylylenediamine by hydrogenation of m-xylylenenitrile under the ammonia-contacting condition, which adopts a Ni or Co catalyst loaded by diatomite, activated carbon, alumina or silica and added with assistants of Re, Cu, Ru, Fe and the like, and can completely convert m-xylylenediamine in a trickle bed reactor, wherein the selectivity of the m-xylylenediamine can reach 98.6%.
The catalyst can also be added with an auxiliary agent to improve the catalytic activity and inhibit side reactions, thereby improving the yield of m-xylylenediamine. CN102029160 discloses a nickel catalyst supported on alumina, in which co-catalysts of copper, cobalt, iron, zinc and the like are added, so that isophthalonitrile can be completely converted under a relatively mild condition, and the selectivity of m-xylylenediamine reaches 98.8%. CN103539676 discloses a method for preparing m-xylylenediamine, which adopts an alumina-supported nickel-based catalyst with concentrated pore distribution, and a molybdenum component is added in the catalyst to inhibit the generation of macromolecular aggregates and prolong the service life. CN101062898 discloses a method for making a hollow fiber membraneMixing xylene and liquid ammonia as solvent, using Ni/MgO-SiO2The catalyst and the two-stage hydrogenation process are used for completely converting m-phthalonitrile into m-xylylenediamine, the total yield of the m-xylylenediamine is 99.5 percent, the addition amount of MgO accounts for 1 to 2 percent of the total mass of the catalyst, the introduction of the MgO reduces the acidity of the catalyst, inhibits the generation of polycondensate, prolongs the service life of the catalyst, and improves the hydrogenation yield, but the two-stage hydrogenation process influences the economy of the process.
In conclusion, the supported nickel catalyst and the fixed bed hydrogenation process are adopted to produce m-xylylenediamine, so that the production efficiency and the yield of the target product can be improved, and the method is safe and environment-friendly. The inhibition of the polycondensation side reaction is the key to the improvement of the yield of the target product m-xylylenediamine, which not only requires the development of a hydrogenation catalyst with high activity, high selectivity and long service life, but also requires the improvement of the hydrogenation reaction process.
Disclosure of Invention
The invention aims to provide a method for preparing m-xylylenediamine by hydrogenation of m-phthalonitrile, which overcomes the defects in the prior art and improves the yield of m-xylylenediamine under mild reaction conditions.
Al is generally used in the existing isophthalonitrile hydrogenation process2O3And SiO2As catalyst carriers, they have a certain acidity, and easily promote condensation side reactions, resulting in an increase in by-products and a decrease in the activity or even deactivation of the catalyst. Different from the modification of the catalyst by introducing a small amount of alkaline components (such as MgO) in some prior art, the technical scheme of the invention directly takes the alkaline carrier MgO as the main component and introduces a small amount of Al2O3The surface area of the carrier is improved, the dispersion of the active component on the carrier is promoted, and the surface acidity and alkalinity of the catalyst are adjusted to adapt to the hydrogenation requirement of the isophthalonitrile, so that the ideal target product selectivity is obtained.
By adopting the technical scheme of the invention, the isophthalonitrile can be converted by 100% through a single-stage hydrogenation process under mild reaction conditions, the yield of the m-xylylenediamine can reach 100% at most, and the method can be suitable for industrial continuous production.
The technical scheme of the invention is as follows:
a method for preparing m-xylylenediamine by hydrogenation of m-phthalonitrile is characterized in that: pumping an isophthalonitrile solution dissolved in a mixed solvent into a bed layer filled with a Ni/MgAlO catalyst by adopting a fixed bed reactor, wherein the temperature is 60-140 ℃, the pressure is 1.0-8.0 MPa, and the mass space velocity of isophthalonitrile is 0.1-5 h-1And reacting the isophthalonitrile with hydrogen to generate m-xylylenediamine under the condition that the molar ratio of the hydrogen to the isophthalonitrile is 5-50: 1.
The mixed solvent is prepared by mixing one or a mixture of N, N-dimethylformamide, N-dimethylacetamide and tetrahydrofuran with one or a mixture of m-xylylenediamine, piperidine, isopropylamine, butylamine, triethylamine, ethanolamine and aniline. The mass percentage concentration of the phthalonitrile in the phthalonitrile solution is 2-20%, preferably 3-15%.
The mass space velocity of the isophthalonitrile solution is 0.1-5 h based on isophthalonitrile-1Preferably 0.25 to 2 hours-1。
The molar ratio of the hydrogen to the isophthalonitrile is 5-50: 1, preferably 10-20: 1.
The reaction temperature is 60-140 ℃, and preferably 90-110 ℃.
The reaction pressure is 1.0-8.0 MPa, preferably 3.0-5.0 MPa.
The mass percentage of the metallic nickel in the Ni/MgAlO catalyst is 50-80%, preferably 60-70%, the mass percentage of the MgO is 20-50%, preferably 30-40%, and the Al content is2O3The content of (b) is 0.5-15% by mass, preferably 1-10% by mass.
The Ni/MgAlO catalyst is prepared by adopting a coprecipitation method. The catalyst needs to be reduced with hydrogen before use.
Detailed Description
The present invention is described below by way of specific examples, but the scope of the present invention is not limited to the specific examples.
Example 1
29.7g of Ni (NO) were weighed3)2·6H2O、19.1g Mg(NO3)2·6H2O and 7.4g Al (NO)3)3·9H2Dissolving O in water to prepare 100ml solution; another 24.1g of Na is taken2CO3Dissolved in water to make 100ml solution. Dropping the two solutions into 200ml of distilled water simultaneously under stirring to generate green precipitate, washing the precipitate with distilled water, adding 200ml of n-butanol, evaporating to dryness in a water bath, drying in a 393K oven, tabletting, crushing, sieving to obtain 20-40 meshes, reducing the catalyst precursor particles in 723K flowing hydrogen for 2h, and reducing hydrogen GSVH for 1000h-1Then at room temperature with a solution containing 0.5% O2/N2And passivating the mixed gas to obtain the catalyst A.
Example 2
29.7g of Ni (NO) were weighed3)2·6H2O、22.3g Mg(NO3)2·6H2O and 3.7g Al (NO)3)3·9H2Dissolving O in water to prepare 100ml solution; another 23.8g of Na is taken2CO3Dissolved in water to make 100ml solution. Dropping the two solutions into 200ml of distilled water simultaneously under stirring to generate green precipitate, washing the precipitate with distilled water, adding 200ml of n-butanol, evaporating to dryness in a water bath, drying in a 393K oven, tabletting, crushing, sieving to obtain 20-40 meshes, reducing the catalyst precursor particles in 723K flowing hydrogen for 2h, and reducing hydrogen GSVH for 1000h-1Then 0.5% O at room temperature2/N2And passivating the mixed gas to obtain a catalyst B.
Example 3
29.7g of Ni (NO) were weighed3)2·6H2O、23.9g Mg(NO3)2·6H2O and 1.8gAl (NO)3)3·9H2Dissolving O in water to prepare 100ml solution; another 23.6g of Na is taken2CO3Dissolved in water to make 100ml solution. Dropping the above two solutions into 200ml distilled water under stirring to generate green precipitate, washing the precipitate with distilled water, adding 200ml n-butanol, evaporating in water bath, oven drying in 393K oven, tabletting, crushing, sieving to obtain 20-40 mesh, and making the catalyst precursor particles in flowing hydrogen gas for 72 daysReducing for 2h with 3K, hydrogen GSVH 1000h-1Then 0.5% O at room temperature2/N2And passivating the mixed gas to obtain the catalyst C.
Example 4
The hydrogenation evaluation reaction of the isophthalonitrile is carried out in a fixed bed reactor, 3ml of catalyst A is filled in the middle of a fixed bed reaction tube with the diameter of 10mm, the upper part and the lower part of the fixed bed reaction tube are filled with quartz sand with the same mesh number as that of catalyst particles, and a high-pressure micro pump is adopted to fill isophthalonitrile solution, wherein the solution comprises the following components in percentage by mass: 12 percent of isophthalonitrile, 5 percent of triethylamine, 83 percent of N, N-dimethylformamide are pumped into a reactor, mixed with hydrogen and then pass through a catalyst bed layer, the reaction temperature is 80 ℃, the hydrogen pressure is 3MPa, and the mass space velocity of the isophthalonitrile is 0.25h-1The molar ratio of hydrogen to isophthalonitrile was 20: 1. The product solution was collected and analyzed by gas chromatography. The conversion of isophthalonitrile was 100%, and the selectivity of m-xylylenediamine was 97.8%.
Example 5
According to the procedure of example 4, using catalyst B, the isophthalonitrile solution used consists of, in mass%: 10 percent of isophthalonitrile, 20 percent of piperidine and 70 percent of N, N-dimethylformamide, the reaction temperature is 100 ℃, the hydrogen pressure is 4MPa, and the mass space velocity of the isophthalonitrile is 0.5h-1The molar ratio of hydrogen to isophthalonitrile is 15: 1, the conversion of isophthalonitrile is 100%, and the selectivity of m-xylylenediamine is 100%.
Example 6
According to the operation of example 4, the catalyst C is adopted, the mass percent of the isophthalonitrile solution is 8 percent of isophthalonitrile, 10 percent of isopropylamine and 82 percent of N, N-dimethylacetamide, the reaction temperature is 120 ℃, the hydrogen pressure is 6MPa, and the mass space velocity of the isophthalonitrile is 0.5h-1The molar ratio of hydrogen to isophthalonitrile was 20: 1, the conversion of isophthalonitrile was 100%, and the selectivity of m-xylylenediamine was 99.5%.
Example 7
According to the procedure of example 4, using catalyst A, a solution of isophthalonitrile consisting of, in mass%, 8% of isophthalonitrile, 2% of m-xylylenediamine, 90% of N, N-dimethylformamide,the reaction temperature is 90 ℃, the hydrogen pressure is 3MPa, and the mass space velocity of the isophthalonitrile is 0.25h-1The molar ratio of hydrogen to isophthalonitrile was 15: 1, the conversion of isophthalonitrile was 100%, and the selectivity of m-xylylenediamine was 99.0%.
Example 8
According to the operation of example 4, the catalyst B is adopted, the mass percent of the isophthalonitrile solution is 12 percent of isophthalonitrile-6 percent of ethanolamine-82 percent of tetrahydrofuran, the reaction temperature is 120 ℃, the hydrogen pressure is 6MPa, and the mass space velocity of the isophthalonitrile is 0.25h-1The molar ratio of hydrogen to isophthalonitrile was 20: 1, the conversion of isophthalonitrile was 100%, and the selectivity of m-xylylenediamine was 99.3%.
Claims (3)
1. A method for preparing m-xylylenediamine by hydrogenation of m-phthalonitrile is characterized in that: pumping an isophthalonitrile solution dissolved in a mixed solvent into a reactor by adopting a fixed bed reactor, passing the isophthalonitrile solution and hydrogen through a catalyst bed layer filled with a Ni/MgAlO catalyst, and reacting the isophthalonitrile and the hydrogen to generate m-xylylenediamine under the conditions that the temperature is 60-140 ℃, the pressure is 1.0-8.0 MPa, the mass space velocity of the isophthalonitrile is 0.1-5 h < -1 >, and the molar ratio of the hydrogen to the isophthalonitrile is 5-50: 1; the Ni/MgAlO catalyst is prepared by a coprecipitation method, and the catalyst needs to be reduced by hydrogen before use.
2. The method of claim 1, wherein: the mass percentage concentration of the phthalonitrile in the isophthalonitrile solution is 2-20%; the mixed solvent is formed by mixing one or a mixture of N, N-dimethylformamide, N-dimethylacetamide and tetrahydrofuran with one or a mixture of m-xylylenediamine, piperidine, isopropylamine, butylamine, triethylamine, ethanolamine and aniline.
3. The method of claim 1, further comprising: the Ni/MgAlO catalyst comprises 50-80% by mass of metallic nickel, 20-50% by mass of MgO and 0.5-15% by mass of Al2O 3.
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| CN108273507B (en) * | 2018-01-26 | 2020-12-01 | 中南民族大学 | Method for reducing nitrile compound by catalytic hydrogenation |
| CN109456200B (en) * | 2018-11-23 | 2021-07-23 | 万华化学集团股份有限公司 | Preparation method of m-xylylenediamine |
| CN110152642B (en) * | 2019-05-24 | 2022-03-01 | 常州大学 | Catalyst for preparing m-xylylenediamine and application thereof |
| CN112934250B (en) * | 2019-12-11 | 2023-06-09 | 中国科学院大连化学物理研究所 | Nitrile hydrogenation catalyst, preparation and application |
| CN113402396A (en) * | 2020-03-16 | 2021-09-17 | 中国石油化工股份有限公司 | Production method for m-xylylenediamine and co-production of 1, 3-diamine methylcyclohexane |
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| CN101062898A (en) * | 2006-04-26 | 2007-10-31 | 上海博源精细化工有限公司 | Isophthalonitrile catalytic hydrogenation method |
| CN101370289A (en) * | 2007-08-13 | 2009-02-18 | 株式会社Ntt都科摩 | Region estimation system, method and device |
| CN101774928A (en) * | 2010-02-10 | 2010-07-14 | 烟台万华聚氨酯股份有限公司 | Method for preparing m-xylylenediamine |
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| CN101062898A (en) * | 2006-04-26 | 2007-10-31 | 上海博源精细化工有限公司 | Isophthalonitrile catalytic hydrogenation method |
| CN101370289A (en) * | 2007-08-13 | 2009-02-18 | 株式会社Ntt都科摩 | Region estimation system, method and device |
| CN101774928A (en) * | 2010-02-10 | 2010-07-14 | 烟台万华聚氨酯股份有限公司 | Method for preparing m-xylylenediamine |
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