CN101544570B - Method for preparing m-phenylene dimethylamine - Google Patents
Method for preparing m-phenylene dimethylamine Download PDFInfo
- Publication number
- CN101544570B CN101544570B CN2009100309014A CN200910030901A CN101544570B CN 101544570 B CN101544570 B CN 101544570B CN 2009100309014 A CN2009100309014 A CN 2009100309014A CN 200910030901 A CN200910030901 A CN 200910030901A CN 101544570 B CN101544570 B CN 101544570B
- Authority
- CN
- China
- Prior art keywords
- solvent
- catalyst
- catalyzer
- catalyst regeneration
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing m-phenylene dimethylamine, which takes m-phthalonitrile as the raw material for multiphase hydrogenation. The method for preparing m-phenylene dimethylamine is characterized in that continuous hydrogenation is carried out in a slurry reactor or a catalyst regeneration coupling reactor; the lower part of the catalyst regeneration coupling reactor serves as a catalyst regeneration section, and the upper part serves as a hydrogenation reaction section; the mixture of the m-phthalonitrile and solvent and hydrogen contact with catalyst in a reaction zone for continuous hydrogenation reaction, and reaction solution is separated to obtain a target product; and after the liquid-solid separation, the catalyst returns to a catalyst regeneration zone and is continuously rinsed with the solvent for regeneration under the condition with the hydrogen. The method for preparing m-phenylene dimethylamine realizes the continuous hydrogenation of the m-phthalonitrile, has simple process and high equipment utilization ratio, is easy to operate, ensures that the catalyst is not prone to breakage and can be regenerated continuously and reused.
Description
Technical field
The present invention relates to a kind of preparation method of m-xylene diamine, especially be particularly related to a kind of method of Isophthalodinitrile preparation of meta-benzene dimethanamine by continuous hydrogenation reaction.
Background technology
M-xylene diamine (m-Xylylenediamine, abbreviation MXDA, CAS1477-55-0) is a kind of aliphatic amide that contains aromatic nucleus, because its good physics, chemical property are widely used.M-xylene diamine is a kind of low toxicity epoxy curing agent of excellent performance, the ambient cure excellent property, and thermotolerance, water tolerance and chemical resistance are good; It can be used for synthesizing polyamides (MX nylon); It also can be used for synthesis of polyurethane stock yard Xylene Diisocyanate (XDI); It is again a kind of important fine chemical material, is effectively applied to the numerous areas such as a rubber crosslinker, stablizer, plastic material, fibre trimmer, farmingization (medicine) and tensio-active agent.
The main production technique of Isophthalodinitrile (IPN) shortening that adopts prepares m-xylene diamine in the prior art, and catalyst system therefor is generally Raney's nickel (Raney Ni), also claims skeleton nickel, adopts the stirring tank batch production.JP54-41804 discloses a kind of preparation method of m-xylene diamine, the method is used Raney's nickel or thunder Buddhist nun cobalt catalyst, adopts the mixed solvent of low-carbon alcohol and aromatic hydrocarbons, in Autoclave, by the standby m-xylene diamine of Isophthalodinitrile Hydrogenation, hydrogen pressure is up to 11MPa among the embodiment.
Prepare m-xylene diamine by the Isophthalodinitrile shortening, also can adopt fixed-bed reactor.JP2003-327563 discloses a kind of by Aromatic Dinitriles, the method for preparing aromatic series dimethylamine (MXDA) such as the Isophthalodinitrile continuous hydrogenation, use the catalyzer of nickeliferous or cobalt, the concentration of reactant Isophthalodinitrile is 1-10% (weight), in fixed bed (trickle bed) reactor, continuous hydrogenation prepares m-xylene diamine.USP 6,881, and 864 disclose a kind of preparation method of m-xylene diamine secondary hydrogenation, and the method adopts the heterogeneous catalyst of nickeliferous and/or cobalt, in the fixed-bed reactor of two series connection, by the standby m-xylene diamine of Isophthalodinitrile Hydrogenation.The method is characterized in that Isophthalodinitrile in the first reactor, transformation efficiency reaches more than 90%; And then enter the second reactor, and the temperature of reaction of the second reactor is higher more than 10 ℃ than the first reactor, and further hydrogenation reaction to Isophthalodinitrile transformation efficiency reaches more than 99.5%.USP 7,323,597 disclose the method that a kind of continuous hydrogenation of liquid Isophthalodinitrile prepares m-xylene diamine, the method adopts the heterogeneous catalyst take nickel and/or cobalt as main active component, in fixed-bed reactor, under the condition that liquefied ammonia exists, by the standby m-xylene diamine of Isophthalodinitrile Hydrogenation.The a part of liquid material that the method is characterized in that reactor effluent returns reactor inlet as the circulating liquid continuous circulation, and enters reactor after fresh liquid Isophthalodinitrile and fresh liquefied ammonia mix, and hydrogen recycles equally.
Aforesaid method of the prior art, the Isophthalodinitrile fixed bed hydrogenation prepares m-xylene diamine and has the catalyst activity decreased, the problems such as dismounting and activation inconvenience, and traditional stirring tank interrupter method hydrogenation process, each operation all will be through reinforced, displacement, reaction, discharging isoperimetric and the frequent operation step that renews, not only labour intensity is large, catalyst life is short, catalyzer broken loss the easy to wear, and plant factor is low, the hydrogen loss amount is large in the operating process, and conversion unit is at height, frequent blocked operation under the low-pressure state can increase the fatigue strength of reactor, thereby reduce the life-span of reactor, and be difficult to realize automatic production.
The purpose of this invention is to provide a kind of hydrogenation efficiency higher, the method for the standby m-xylene diamine of the Isophthalodinitrile Hydrogenation that continuous catalyst regenerating recycles.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of m-xylene diamine, can overcome intermittent type method of hydrotreating operation steps numerous and diverse, labour intensity is large, catalyzer broken loss the easy to wear, plant factor is low, and the active fall off rate of the existing catalyst of fixed bed hydrogenation becomes fast, the shortcomings such as dismounting and activation and regeneration inconvenience, reach the technique effect of highly effective hydrogenation, transformation efficiency and the selectivity of hydrogenation reaction are high, and solved continuous catalyst regenerating in the Isophthalodinitrile continuous hydrogenation process, the technical problem that recycles, the continuous automatic production of realization m-xylene diamine.
The technical solution adopted in the present invention is as follows:
A kind of preparation method of m-xylene diamine, the heterogeneous hydrogenation take Isophthalodinitrile as raw material, it is characterized in that adopting slurry reactor/catalyst regeneration coupled reactor to carry out continuous hydrogenation, the bottom of described coupled reactor is catalyst regeneration zones, and top is hydroconversion reaction zone; Hydrogen enters coupled reactor through catalyst regeneration zones, and the mixture of Isophthalodinitrile and solvent contacts with the particulate solid catalyzer with the reaction zone of hydrogen at coupled reactor, carries out the continuous hydrogenation reaction; Reaction solution enters continuously separator with catalyzer and carries out liquid-solid the separation; Separate afterreaction liquid and be isolated to again the purpose product; After isolated catalyzer added solvent, the catalyst regeneration zones of coupled reactor was returned in circulation, continuously solvent wash regeneration under the condition that hydrogen exists; Return the catalyst regeneration zones of coupled reactor after the unreacted pressurized with hydrogen; Catalyzer after the regeneration, solvent and hydrogen enter the reaction zone of coupled reactor continuously.
Described slurry reactor/catalyst regeneration coupled reactor is gas-liquid-solid three-phase slurry bubbling bed, and top is hydroconversion reaction zone, and the bottom is catalyst regeneration zones.The present invention uses paste state bed reactor in Isophthalodinitrile hydrogenation, be easy to keep the bed temperature of reaction even, adopts finely grained catalyst, is conducive to diffusion, the migration of reactive material, makes the utilization of granules of catalyst internal surface more abundant; Transformation efficiency and the selectivity of hydrogenation reaction are high; It is convenient that liquid phase continuous feeding and discharging, catalyzer are discharged regeneration.
In described slurry reactor/catalyst regeneration coupled reactor, hydroconversion reaction zone and catalyst regeneration zones are in same slurry bubbling bed bed body, between catalyst regeneration zones and the hydroconversion reaction zone sparger is set, the hydrogen that rises in the breeding blanket enters reaction zone after the sparger redistribution, the solidliquid mixture in the breeding blanket also enters reaction zone through sparger; The hydrogen of reaction zone and solidliquid mixture can not flow into the breeding blanket.Described sparger can be porous plate, and hydrogen and solidliquid mixture in the breeding blanket enter hydroconversion reaction zone through porous plate together; Sparger also can be comprised of porous plate and solid-liquid thrust-augmenting nozzle, hydrogen in the breeding blanket enters hydroconversion reaction zone through porous plate, and the solidliquid mixture in the breeding blanket enters reaction zone through the solid-liquid thrust-augmenting nozzle, and the solid-liquid thrust-augmenting nozzle can be one, also can be many, preferred many solid-liquid thrust-augmenting nozzles.
Described slurry reactor/catalyst regeneration coupled reactor, its reaction zone can be starched the attitude bed with single-stage, also available multistage slurry attitude bed series connection; Preferred plural serial stage.
In the mixture of described Isophthalodinitrile and solvent, Isophthalodinitrile content is 0.2～35% (weight), preferred 2～25% (weight).Wherein said solvent comprises organic amine, aromatic hydrocarbons, low-carbon alcohol, water or their mixture; In the described mixed solvent, organic amine, aromatic hydrocarbons, low-carbon (LC) alcohol and water can be arbitrary proportions, the water of pure and mild 0～40% (weight) of the aromatic hydrocarbons, 30～70% (weight) of the organic amine, 30～70% (weight) that preferred solvent composition is 0～40% (weight).
Described organic amine is selected from one or more in aniline, methylamine, ethamine, quadrol or the phenylenediamine, preferred aniline, phenylenediamine; Described aromatic hydrocarbons is one or more in the aromatic hydrocarbons of 6～9 carbon atoms, preferred toluene, dimethylbenzene, trimethylbenzene; Described low-carbon alcohol is one or more that contain in the alcohol of 1～4 carbon atom, particular methanol, ethanol.
Described particulate solid catalyzer can be the various solid hydrogenation catalysts take nickel or cobalt as main active component, wherein preferred nickel base amorphous alloy catalyzer or Raney's nickel catalyst, and wherein nickel content is 40～90% (weight).Described amorphous alloy catalyst, is 45 ± 1 ° at 2 θ and locates to occur a diffuse maximum (steamed bun shape diffuse scattering peak) in the X-ray diffractogram of this catalyzer take nickel as main active component.The granular size of catalyzer is 1 micron to 1 millimeter, preferred 10～500 microns.
Described m-xylene diamine preparation method, the hydrogenation reaction processing condition are that temperature is 25～120 ℃, and pressure is 0.5～12.0MPa, solid catalyst and liquid material weight ratio 0.005～0.15: 1, hydrogen and liquid material input material volume ratio 100～2000: 1,0.2～6.0 hour reaction times; Preferred reaction process condition is that temperature is 40～100 ℃, and pressure is 1.5～9.0MPa, solid catalyst and liquid material weight ratio 0.02～0.10: 1, hydrogen and liquid material input material volume ratio 200～1500: 1,0.5～4.0 hour reaction times.
Hydrogenation reaction afterreaction liquid carries out liquid-solid the separation in separator with solid catalyst.Described separator can adopt magnetic separator, settlement separator or wet cyclone.
After reaction solution separated with solid catalyst is liquid-solid, reaction solution entered the subsequent products separation system, obtained the purpose product through further separating.Reaction solution mainly is comprised of solvent and purpose product m-xylene diamine, can adopt the methods such as rectifying with purpose product and separated from solvent, obtains purpose product m-xylene diamine; As reaction solution is distilled first desolventizing, then it is sent into the m-xylene diamine rectifying tower, rectifying obtains highly purified m-xylene diamine product.Recirculation is used after the solvent recuperation.
Isolated catalyzer can all enter the breeding blanket of coupled reactor and regenerate, and also can be partial regeneration, and the part circulation enters the reaction zone of coupled reactor, and direct circulation uses.The method that catalyst regeneration adopts is solvent wash regeneration under the condition that hydrogen exists.Cleaning solvent is organic amine, aromatic hydrocarbons, low-carbon alcohol, water or sig water, or their mixture.The condition of catalyst regeneration is 20～120 ℃ of temperature, and pressure is normal pressure～12.0MPa, solid catalyst and liquid solvent weight ratio 0.02～0.35: 1, hydrogen and liquid-solid mixture input material volume ratio 100～2000: 1,0.1～5.0 hour recovery time; Preferred regeneration condition is that temperature is 40～100 ℃, and pressure is 0.5～9.0MPa, solid catalyst and liquid material weight ratio 0.05～0.25: 1, hydrogen and liquid-solid mixture input material volume ratio 200～1500: 1,0.2～4.0 hour recovery time.
M-xylene diamine preparation method of the present invention recycles after with the hydrogen gas compressor supercharging from coupled reactor top unreacted hydrogen out in the hydrogenation reaction, namely goes back to the breeding blanket of slurry reactor/catalyst regeneration coupled reactor after the supercharging.
M-xylene diamine preparation method of the present invention adds ammonia in the Isophthalodinitrile hydrogenator, can suppress the generation of by product in the hydrogenation reaction, the yield of corresponding raising m-xylene diamine, and ammonia and Isophthalodinitrile raw materials components mole ratio are 0～1.5: 1.
According to m-xylene diamine preparation method of the present invention, can realize the continuous hydrogenation of Isophthalodinitrile, transformation efficiency and selectivity are good, and the Isophthalodinitrile transformation efficiency is near 100%, and hydrogenation efficiency is high, continuous catalyst regenerating, recycles.Compare with existing tank reactor or fixed bed hydrogenation technique, not only hydrogen utilization ratio is high, and plant factor is high, and production efficiency is high, and catalyzer fragmentation not easy to wear, and catalyst life is long, and catalyst separating, regeneration facility can realize automatic production.
Below in conjunction with accompanying drawing, describe the present invention by the embodiment example.Scope of the present invention is not limited with embodiment, but is limited by claim.
Description of drawings
The process flow diagram of the continuous hydrogenation method under the whole continuous reproduction process conditions of Fig. 1 catalyzer
The process flow diagram of the continuous hydrogenation method under Fig. 2 catalyst member continuous reproduction process condition
Embodiment
Hydrogen enters from the bottom, breeding blanket of reaction/regenerative coupling reactor 2, reaction raw materials (Isophthalodinitrile and solvent) and live catalyst enter from the middle part (reaction zone bottom) of reaction/regenerative coupling reactor 2, carry out the reaction of Isophthalodinitrile continuous hydrogenation, reaction mass is realized gas-liquid separation at coupled reactor 2 headspaces.The tail gas of discharging from reactor 2 tops recycles after i.e. compressed machine 1 supercharging of unreacted hydrogen; Enter liquid-solid separator 3 from the liquid-solid mixture of reactor 2 top extraction and carry out liquid-solid separation, solid catalyst is separated with reaction solution.Isolated solid catalyst adds an amount of solvent, and regenerating in the bottom, breeding blanket that is delivered to reaction/regenerative coupling reactor 2 with pump 4, directly enters reaction zone after the regeneration; The isolated reaction solution that contains purpose product m-xylene diamine enters follow-up Distallation systm (not marking among the figure) after further filtering, obtain m-xylene diamine behind the rectifying desolvation.
In the above-mentioned technique, reaction raw materials consists of Isophthalodinitrile 28% (weight), methyl alcohol 36% (weight) and toluene 36% (weight), uses commercially available amorphous nickel catalyzer, and its nickel content is 88% (weight).200 kg/hrs of reaction raw materials inlet amounies, adding quantity of solvent during isolated solid catalyst regeneration is 80 kg/hrs, solvent composition is, methyl alcohol 50% (weight) and toluene 50% (weight), hydrogen recycle amount 120 standard cubes m/h.Solid catalyst and liquid weight be than 0.08: 1 in the reaction zone, 67 ℃ of hydrogenation reaction temperature, 2 hours residence time in reaction zone of pressure 5.0MPa, material.The catalyst regeneration condition is: 62 ℃ of regeneration temperatures, and pressure 5.0MPa, solid catalyst and weight of solvent were than 0.22: 1 in the breeding blanket, and 1 hour recovery time, regenerated solvent forms: methyl alcohol 50% (weight) and toluene 50% (weight).
Prepare m-xylene diamine through aforesaid method, the Isophthalodinitrile transformation efficiency is 100%, and the m-xylene diamine yield is 93.6%.
Reaction result is as shown in table 1.
Table 1 Isophthalodinitrile continuous hydrogenation prepares the m-xylene diamine reaction result
Embodiment 7
Embodiment 7 adopts method of the present invention by the Isophthalodinitrile preparation of meta-benzene dimethanamine by continuous hydrogenation reaction, and its technical process as shown in Figure 2.
Hydrogen enters from the bottom, breeding blanket of reaction/regenerative coupling reactor 2, reaction raw materials (Isophthalodinitrile and solvent) and live catalyst enter from the middle part (reaction zone bottom) of reaction/regenerative coupling reactor 2, carry out the reaction of Isophthalodinitrile continuous hydrogenation, reaction mass is realized gas-liquid separation at reactor 2 headspaces.The tail gas of discharging from reactor 2 tops recycles after i.e. compressed machine 1 supercharging of unreacted hydrogen; Enter liquid-solid separator 3 from the liquid-solid mixture of reactor 2 top extraction and carry out liquid-solid separation, solid catalyst is separated with reaction solution.Isolated solid catalyst, a part of direct circulation returns reaction zone, and after a part added an amount of solvent, regenerating in the bottom, breeding blanket that is delivered to reaction/regenerative coupling reactor 2 with pump 4, directly enters reaction zone after the regeneration; The isolated reaction solution that contains purpose product m-xylene diamine enters follow-up Distallation systm (not marking among the figure) after further filtering, obtain m-xylene diamine behind the rectifying desolvation.
Claims (10)
1. the preparation method of a m-xylene diamine, the heterogeneous hydrogenation take Isophthalodinitrile as raw material, it is characterized in that adopting slurry reactor/catalyst regeneration coupled reactor to carry out continuous hydrogenation, described slurry reactor/catalyst regeneration coupled reactor is gas-liquid-solid three-phase slurry bubbling bed, the bottom of coupled reactor is catalyst regeneration zones, top is hydroconversion reaction zone, hydroconversion reaction zone and catalyst regeneration zones are in same slurry bubbling bed bed body, between catalyst regeneration zones and the hydroconversion reaction zone sparger is set, hydrogen and solidliquid mixture in the breeding blanket enter reaction zone through sparger; Hydrogen enters coupled reactor through catalyst regeneration zones, and the mixture of Isophthalodinitrile and solvent contacts with the particulate solid catalyzer with the reaction zone of hydrogen at coupled reactor, carries out the continuous hydrogenation reaction; Reaction solution enters continuously separator with catalyzer and carries out liquid-solid the separation; Separate afterreaction liquid and be isolated to again the purpose product; After isolated catalyzer added solvent, the catalyst regeneration zones of coupled reactor was returned in circulation, continuously solvent wash regeneration under the condition that hydrogen exists; Return the catalyst regeneration zones of coupled reactor after the unreacted pressurized with hydrogen; Catalyzer after the regeneration, solvent and hydrogen enter the reaction zone of coupled reactor continuously.
2. the preparation method of m-xylene diamine according to claim 1, it is characterized in that: the sparger between described catalyst regeneration zones and the hydroconversion reaction zone is porous plate, or is comprised of porous plate and solid-liquid thrust-augmenting nozzle.
3. the preparation method of m-xylene diamine according to claim 1, it is characterized in that: in the mixture of described Isophthalodinitrile and solvent, the weight percentage of Isophthalodinitrile is 0.2～35%; Described solvent is organic amine, aromatic hydrocarbons, contains alcohol or the water of 1～4 carbon atom, or their mixture.
4. the preparation method of m-xylene diamine according to claim 3, it is characterized in that: described organic amine is selected from one or more in aniline, methylamine, ethamine, quadrol, the phenylenediamine; Described aromatic hydrocarbons is one or more in the aromatic hydrocarbons of 6～9 carbon atoms; Described low-carbon alcohol is methyl alcohol or ethanol.
5. the preparation method of m-xylene diamine according to claim 1, it is characterized in that: described particulate solid catalyzer is Raney's nickel or nickel base amorphous alloy catalyzer, wherein in the X-ray diffractogram of nickel base amorphous alloy catalyzer, be 45 ± 1 ° at 2 θ and locate to exist a diffuse maximum; The weight percentage of nickel is 40～90% in the described catalyzer; Granular size is 1 micron to 1 millimeter.
6. the preparation method of m-xylene diamine according to claim 1, it is characterized in that: described hydrogenation reaction processing condition are 25～120 ℃ of temperature, pressure 0.5～12.0MPa, solid catalyst and liquid material weight ratio 0.005～0.15: 1, hydrogen and liquid material volume ratio 100～2000: 1,0.2～6.0 hour reaction times.
7. the preparation method of m-xylene diamine according to claim 1 is characterized in that: described separator employing magnetic separator, settlement separator or wet cyclone.
8. the preparation method of m-xylene diamine according to claim 1 is characterized in that: described catalyzer solvent wash regeneration refers to that isolated whole catalyzer adds the catalyst regeneration zones that coupled reactor is returned in circulation behind the solvent; Perhaps circulate behind the isolated partially catalyzed agent adding solvent and return the catalyst regeneration zones of coupled reactor, all the other catalyzer direct circulations return the reaction zone of coupled reactor.
9. according to claim 1 or the preparation method of 8 described m-xylene diamines, it is characterized in that: the regeneration of catalyzer solvent wash, described solvent is organic amine, aromatic hydrocarbons, low-carbon alcohol, water or sig water, or their mixture; Described organic amine is selected from one or more in aniline, methylamine, ethamine, quadrol, the phenylenediamine; Described aromatic hydrocarbons is one or more in the aromatic hydrocarbons of 6～9 carbon atoms; Described low-carbon alcohol is one or more that contain in the alcohol of 1～4 carbon atom; The catalyst regeneration condition is 25～120 ℃ of temperature, pressure 0.5～12.0MPa, solid catalyst and liquid solvent weight ratio 0.02～0.35: 1,0.1～5.0 hour recovery time.
10. the preparation method of m-xylene diamine according to claim 1 is characterized in that: in the described continuous hydrogenation reaction, pass into ammonia in coupled reactor, ammonia and Isophthalodinitrile raw materials components mole ratio are 0～1.5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100309014A CN101544570B (en) | 2009-04-17 | 2009-04-17 | Method for preparing m-phenylene dimethylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100309014A CN101544570B (en) | 2009-04-17 | 2009-04-17 | Method for preparing m-phenylene dimethylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101544570A CN101544570A (en) | 2009-09-30 |
| CN101544570B true CN101544570B (en) | 2013-01-02 |
Family
ID=41191973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100309014A Active CN101544570B (en) | 2009-04-17 | 2009-04-17 | Method for preparing m-phenylene dimethylamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101544570B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721706B (en) * | 2012-10-15 | 2016-08-03 | 中国石油化工股份有限公司 | Purification of terephthalic acid palladium carbon catalyst reduction washing methods |
| CN109293511B (en) * | 2018-11-12 | 2020-08-25 | 西南化工研究设计院有限公司 | Method for preparing methyl methacrylate by condensing methyl propionate and formaldehyde aldol |
| CN113578208A (en) * | 2021-08-17 | 2021-11-02 | 葫芦岛连石化工有限责任公司 | Environment-friendly production system for producing phenylenediamine through three-phase continuous hydrogenation |
| CN114671769A (en) * | 2022-04-24 | 2022-06-28 | 河南尤尼特化工新材料有限公司 | Process for continuously producing m-xylylenediamine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285343A (en) * | 1999-08-19 | 2001-02-28 | 中国石油化工集团公司 | Process for preparation of metabenzenedimethanamine |
| CN101062898A (en) * | 2006-04-26 | 2007-10-31 | 上海博源精细化工有限公司 | Isophthalonitrile catalytic hydrogenation method |
| CN101337893A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Process for preparation of meta-benzene dimethanamine by continuous hydrogenation reaction |
| CN101337894A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Process for preparation of meta-benzene dimethanamine by continuous hydrogenation reaction in stirring vessel |
-
2009
- 2009-04-17 CN CN2009100309014A patent/CN101544570B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285343A (en) * | 1999-08-19 | 2001-02-28 | 中国石油化工集团公司 | Process for preparation of metabenzenedimethanamine |
| CN101062898A (en) * | 2006-04-26 | 2007-10-31 | 上海博源精细化工有限公司 | Isophthalonitrile catalytic hydrogenation method |
| CN101337893A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Process for preparation of meta-benzene dimethanamine by continuous hydrogenation reaction |
| CN101337894A (en) * | 2008-08-08 | 2009-01-07 | 德纳（南京）化工有限公司 | Process for preparation of meta-benzene dimethanamine by continuous hydrogenation reaction in stirring vessel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101544570A (en) | 2009-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101337894B (en) | Process for preparation of meta-benzene dimethanamine by continuous hydrogenation reaction in stirring vessel | |
| CN101337893B (en) | Process for preparation of meta-benzene dimethanamine by continuous hydrogenation reaction | |
| CN103145974B (en) | Method of preparing primary amine by ammonification of alcoholic hydroxyl group | |
| CN101544570B (en) | Method for preparing m-phenylene dimethylamine | |
| CN101429139B (en) | Process for producing dicyclohexyl methyl hydride diisocyanate and its midbody | |
| CN112661625B (en) | Preparation process of succinic acid | |
| CN105032428A (en) | Preparation method for synthesizing catalyst by microwave heating and one-step cyclohexylamine synthesizing method by catalyst prepared based on preparation method | |
| CN104693434A (en) | Production method for continuously synthesizing polyether amine through static bed | |
| CN101891718B (en) | Continuous production process for preparing succinyl oxide by maleic anhydride hydrogenation | |
| CN105348510A (en) | Method for continuously producing amino-terminated polyether | |
| CN102070464B (en) | Method for producing phenylene diamine by performing hydrogenation reduction on mixed dinitrobenzene with palladium catalyst | |
| CN101239957B (en) | Method for synthesizing N-methylpiperazine | |
| CN114380698B (en) | Method for synthesizing methylcyclohexanediamine by selective hydrogenation of diaminotoluene by continuous method | |
| CN116836067A (en) | Method for preparing diaminodiphenyl ether by continuous catalytic hydrogenation | |
| CN101890323A (en) | Reactor for preparing succinyl oxide by maleic anhydride hydrogenation | |
| CN103965055B (en) | The synthetic method of Isopropylamine | |
| CN102603539B (en) | Method and device for recycling catalyst particles in crude toluene diamine | |
| CN115178191A (en) | Polyether amine continuous production system and method | |
| CN115449068A (en) | Method for preparing amino-terminated polyether by continuous hydroamination | |
| CN101245060A (en) | Method for producing N-alkyl-(3,4-methylenedioxy) aniline | |
| CN102180771A (en) | Preparation method for 3-methyl-3-butene-1-alcohol | |
| CN113797929A (en) | Solid catalyst for catalyzing synthesis of butanediamine, method for preparing butanediamine by using solid catalyst and system device | |
| CN106957420A (en) | A kind of method that Aethoxy Sklerol direct aminatin prepares polyetheramine | |
| CN102603486A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN101817753B (en) | Preparation method of N-(3-aminopropyl)-1,3-propane diamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 210047 Jiangsu city of Nanjing province Nanjing Chemical Industrial Park, Bailong Road No. 2 Patentee after: Jiangsu Dena chemical Limited by Share Ltd Patentee after: Jiangsu Tianyin Chemical Industry Co., Ltd. Address before: 210047 Jiangsu city of Nanjing province Nanjing Chemical Industrial Park, Bailong Road No. 2 Patentee before: Dana (Nanjing) Chemical Co. Ltd. Patentee before: Jiangsu Tianyin Chemical Industry Co., Ltd. |