CN108623476A - A kind of nitro compound Hydrogenation for amine product method - Google Patents
A kind of nitro compound Hydrogenation for amine product method Download PDFInfo
- Publication number
- CN108623476A CN108623476A CN201810690169.2A CN201810690169A CN108623476A CN 108623476 A CN108623476 A CN 108623476A CN 201810690169 A CN201810690169 A CN 201810690169A CN 108623476 A CN108623476 A CN 108623476A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- stirred tank
- fixed bed
- tank 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.)
- Granted
Links
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Nc1ccccc1 Chemical compound Nc1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N [O-][N+](c1ccccc1)=O Chemical compound [O-][N+](c1ccccc1)=O LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a kind of nitro compound Hydrogenations for the method for amine product.This method is realized by the continuous reaction system that stirred tank reactor and fixed bed reactors form, the gas phase discharging of tank reactor continues to react into fixed bed reactors, and a small amount of liquid phase in bottom also continues to react after filtering out catalyst into fixed bed reactors.This method can greatly improve nitro compound conversion ratio by the cooperation of two class reactors and the use of different activities catalyst, while also greatly overcome the adverse effect of excessive hydrogenation.
Description
Technical field
The invention belongs to hydrogenation synthesis fields, and in particular to a kind of nitro compound Hydrogenation for amine product method.
Background technology
Aniline is a kind of oily liquids, has extensive use in medicine, pigment and rubber chemicals production.Currently, nitro
Benzene catalytic hydrogenation is the main method for producing aniline, and reaction process is schematically as follows:
Catalytic Hydrogenation of Nitrobenzene includes mainly two kinds of techniques of gas phase hydrogenation and liquid-phase hydrogenatin.Early stage mostly uses gas phase fixed bed
Add hydrogen, the technological operation is easy, is not required to separating catalyst, but because moving heat limitation, it is difficult to which enlargement has been rarely employed.Subsequently
Liquid-phase hydrogenatin technique is gradually risen, and wherein E.I.Du Pont Company's patent US4185036 discloses a kind of slurry bed system liquid-phase hydrogenatin technique, should
Technique uses Multistage tower-type reactor, can obtain higher nitrobenzene conversion rate, but its slurry bed system bottom end nitro phenenyl concentration is high
Up to 40%, it is easy accelerator activator inactivation.Tar is easy tod produce under the conditions of the nitrobenzene of patent EP2471768 discovery high concentrations,
This can cause catalyst inactivation, catalyst life to shorten, and production cost dramatically increases.In addition, in aforementioned Du Pont's technique, catalysis
Agent needs all extraction, reactor is returned again to after concentrated, the cycle of a large amount of catalyst pulps inevitably causes part
Catalyst loss.
ICI Company patent US3270057 discloses a kind of liquid phase continuous catalytic hydrogenation technique, which uses product aniline
As solvent, concentration of aniline is up to 95% in reaction solution, and reaction heat vaporizes the benzene taken out of, but prepared under this condition by reaction solution
Still contain 0.6% unreacted nitrobenzene in amine, and the by-product of benzene ring hydrogenation is more.
BASF AG patent US6350911 uses stirred tank reactor, the Pt loaded with activated carbon (containing hydroxide)
Catalytic Hydrogenation of Nitrobenzene reaction is carried out for catalyst, reaction heat is removed by the heat exchanger tube being arranged in reaction kettle, though the technique
Reaction conversion ratio is so improved, but the problem of (up to 1000ppm) higher there are still by-products content.
The problem of for above-mentioned hydrogenation of chloronitrobenzene technique, a kind of new process need to be sought, to improve hydrogenation of chloronitrobenzene
The flexibility of reactor operating procedure also reduces the inactivation probability and most of catalyst while improving the conversion ratio of nitrobenzene
Limits reduce side reaction.
Invention content
Present invention aims at a kind of nitro compound Hydrogenations of offer for the method for amine product, has nitro compound
The advantage that high conversion rate, catalyst inactivation probability be low, high selectivity, by-product are few, aniline is prepared particularly suitable for hydrogenation of chloronitrobenzene.
In order to achieve the above objectives, technical scheme is as follows:
For the method for amine product, this method is anti-by stirred tank reactor and fixed bed for a kind of nitro compound Hydrogenation
The continuous reaction system that device forms is answered to realize, system includes two stages of reaction:(1) raw material is added in stirred tank reactor
Hydrogen reacts;(2) discharging of stirred tank reactor gas phase continues hydrogenation reaction into fixed bed reactors, while stirred tank reacts
Device bottom produces a small amount of liquid phase, also continues hydrogenation reaction into fixed bed reactors after filtering out catalyst.
Above-mentioned reaction system passes through different living in nitro-compound concentration in control tank reactor and two reactors
Property catalyst (catalyst activity is high in reaction kettle, and catalyst activity is low in fixed bed) mutual cooperation, it is anti-autoclave can be controlled
It answers nitro-compound concentration in device liquid phase to be maintained at 1-10wt%, avoids excessive hydrogenation from generating the by-products such as cyclohexanone, cyclohexylamine, not
The hydrogenation reaction of completion is further continued for completing after entering fixed bed.The technology controlling and process of the system is more flexible, and substantially extends
Catalyst service life, while high nitro compound conversion ratio and good selectivity of product can be obtained.
In the present invention, stirred tank reactor top gas phase product exit and fixed bed reactors lower part in continuous reaction system
It is connected;Liquid phase discharge port is arranged in stirred tank reactor bottom, is sequentially connected delivery pump, catalyst filter to fixed bed bottom
Atomizer is arranged in feed inlet, feed inlet upper end;Fixed bed top gas phase discharge port is sequentially connected product condenser and chromatography device.
In the present invention, stage (1) nitro compound is mixed into stirred tank reactor after preheating with water, catalyst,
Hydrogen enters reactor lower part by gas distributor, and liquid phase nitro-compound concentration is maintained at 1- in kettle in reaction process
10wt%, preferably 3-5wt%.When nitro-compound concentration is less than 1wt%, the concentration of the product amine in reaction kettle is higher, easily
Excessive hydrogenation generates a large amount of by-products;When nitro-compound concentration is higher than 10wt%, nitro compound is in catalyst surface
Absorption can inhibit further to add hydrogen, while the tar generated can cause catalyst inactivation, so that catalyst life is shortened, production cost
Increase.
In the present invention, stage (1) hydrogen is 2-20mol%, preferably 5- relative to the overrate of nitro compound
15mol%.When hydrogen overrate is less than 2mol%, nitro compound adds hydrogen incomplete, and conversion ratio reduces, when hydrogen overrate
When higher than 20mol%, excessive hydrogenation generates a large amount of by-products in reaction kettle, and selectivity of product reduces.
In the present invention, the stage (1) uses noble metal, nickel, copper, zinc, aluminium hydrogenation catalyst, preferably noble metal catalyst, more
It is preferred that palladium, platinum catalyst, catalyst concn is 0.2-5wt%, preferably 1-2wt% in reaction kettle.When catalyst concn is less than
When 0.2wt%, reaction rate is slower, and equipment capacity is caused to reduce, and does not utilize enlarged production, when catalyst concn is higher than
When 5wt%, catalyst suspension is deteriorated, and catalyst is easy coalescence inactivation.
In the present invention, stage (1) reactor bottom produces the 0.1-2wt% that amount of liquid phase is liquid phase feeding amount.If produced quantity
Less than the 0.1wt% of inlet amount, heavy constituent is accumulated in reaction kettle, and catalyst deactivation rate is caused to speed, and the service life shortens, if adopting
Output is more than the 2wt% of inlet amount, and the catalytic amount that heavy constituent is taken out of increases, and catalyst loss amount increases, and production cost is notable
Increase.
In the present invention, 160-250 DEG C of stage (1) reactor temperature, preferably 200-220 DEG C, pressure 5-20bar.Work as temperature
Degree is less than 160 DEG C, and reaction rate is slower, influences production efficiency, is unfavorable for enlarged production, when temperature is higher than 250 DEG C, nitro
Compound hydrogenation capability enhances, and generates easy excessive hydrogenation and generates by-product, leads to selectivity reduction and later separation is difficult.
The stage (2) of the process of the present invention is gas-solid reaction, and the fixed bed reactors are one or more levels group
It closes, reduces back-mixing of the material in reactor, while pursuing nitro compound maximum conversion rate, also reduce to greatest extent
The excessive hydrogenation of product.
In the present invention, stage (2) feeding temperature is 150-220 DEG C, preferably consistent with stirred tank reactor drop temperature;Gu
Fixed bed reactor pressure 1-20bar, air speed are 0.5-80/hr (nitrobenzene quality/catalyst quality).
In the present invention, the stage (2) uses only makes nitro hydrogenation under reaction condition at this stage and phenyl ring is not added with the low of hydrogen
Active catalyst, preferably Cu-series catalyst, (preparation method is with reference to patent for more preferable cu-zn-al alloy catalyst
CN106000408A), this can substantially weaken excessive hydrogenation problem, reduce by-product to greatest extent.Loaded catalyst is such
The conventional filling amount of fixed bed reactors.
In the present invention, reaction heat is taken away by boiler water cycle system, and according to the full of production requirement by-product 0.3-2MPa
And steam, improve heat utilization ratio.
In the present invention, the nitro compound is selected from aromatic nitro compound, preferably between/paradinitrobenzene, nitro
It is one or more in toluene, nitrobenzene, 2- meta-xylenes, nitronaphthalene, more preferable nitrobenzene.
Heretofore described pressure is gauge pressure.
The positive effect of the present invention is:
(1) continuous reaction system for using tank reactor and fixed bed reactors composition, by controlling still reaction
In device in nitro-compound concentration and two kinds of reactors different activities catalyst mutual cooperation, the technique for making hydrogenation process
Control is more flexible;
(2) use this method product purity higher, nitrobenzene is less than 10ppm in product;
(3) use this method catalyst inactivation probability low;
(4) this method high selectivity is used, excessive hydrogenation by-product is less than 130ppm in product.
Description of the drawings
Fig. 1 is the nitro compound Hydrogenation of the present invention for the reaction system schematic diagram of amine product.
In Fig. 1:1. feedstock transportation pumps, 2. water delivery pumps, 3. feed preheaters, 4. stirred tank reactors, 5. fixed beds are anti-
Answer device, 6. product condensers, 7. catalyst filters, 8. reaction solution delivery pumps, 9. chromatography devices.
Specific implementation mode
Illustrate that technical scheme of the present invention, embodiment give specific embodiment and tool with specific embodiment below
The operating process of body, but protection scope of the present invention is not limited to following embodiments.
Using reaction system as shown in Figure 1, wherein stirred tank volume 0.17m3, diameter 500mm, high 650mm, using certainly
Suction agitating paddle, a diameter of 155mm;Fixed bed diameter 300mm, catalyst packing height 3000mm;Catalyst filter is gold
Belong to sintering filter stick form;Reactor product cooler byproduct steam.
Product analysis instrument:Gas chromatograph is Agilent 7820A, the capillary column (μ of DB-5,30m × 0.25mm × 0.25
M), 60 DEG C of initial temperature are kept for 1 minute;80 DEG C are risen to the rate of 10 DEG C/min, is kept for 1 minute;Again with the speed of 15 DEG C/min
Rate rises to 250 DEG C, is kept for 8 minutes.Carrier gas is high-purity N2, split ratio 30:1, bypass flow 39mL/min.Carrier gas flux 20mL/
Min starts waiting for time 2min, 250 DEG C, detector FID of injector temperature, 260 DEG C of detector temperature, 0.2 μ L of sample size.
Embodiment 1
Nitrobenzene is sent into stirred tank reactor 4, flow by nitrobenzene delivery pump 1 after the heating of nitrobenzene preheater 3
65kg/hr;Water is sent into stirred tank reactor 4, water flow 55kg/hr by water delivery pump 2;Hydrogen is passed through stirred tank reactor
4, flow 1664mol/hr;Using the Pt/Pd catalyst of load type active carbon, a concentration of 1wt% in reaction kettle.Pressure 17bar,
At 200 DEG C of temperature, nitrobenzene, which is reacted with hydrogen in stirred tank reactor, generates aniline and water.
Stirred tank reactor gas phase discharges into fixed bed reactors 5, and the reaction was continued, and 0.6kg/hr is pressed in stirred tank bottom
Flow produce liquid material, after filter 7 filters out catalyst, be sprayed to after fixed bed bottom end mix with gas phase continuation instead
It answers.Using cu-zn-al alloy catalyst (preparation method with reference to patent CN106000408A) in fixed bed, loadings 0.8kg,
Continue hydrogenation reaction at pressure 2bar, 200 DEG C of inlet temperature, the gaseous products of extraction enter chromatography device by condenser 6 and obtain
To aniline crude product.
Continuous-stable operates 3 months device under these conditions.Liquid phase nitro phenenyl concentration is about in its stirred tank reactor
3%, fixed bed adiabatic temperature rises 33 DEG C, and air speed is 2.4/hr (nitrobenzene quality/catalyst quality) to oil in chromatography device in bed
It is mutually crude product sampling analysis, wherein nitrobenzene is 2.5ppm, and the by-products such as cyclohexanone, the cyclohexylamine of excessive hydrogenation always contain
Amount is 120ppm.
Embodiment 2
Nitrobenzene is sent into stirred tank reactor 4, flow by nitrobenzene delivery pump 1 after the heating of nitrobenzene preheater 3
65kg/hr;Water is sent into stirred tank reactor 4, water flow 55kg/hr by water delivery pump 2;Hydrogen is passed through stirred tank reactor
4, flow 1617mol/hr;Reaction kettle uses the Pt/Pd catalyst of load type active carbon, a concentration of 0.2wt%.Pressure 17bar,
At 250 DEG C of temperature, nitrobenzene, which is reacted with hydrogen in stirred tank reactor, generates aniline and water.
Stirred tank reactor gas phase discharges into fixed bed reactors 5, and the reaction was continued, in stirred tank bottom by 2kg/hr's
Flow produces liquid material, after filter 7 filters out catalyst, is sprayed to after fixed bed bottom end is mixed with gas phase that the reaction was continued,
Using using cu-zn-al alloy catalyst (preparation method is with reference to patent CN106000408A) in fixed bed, loaded catalyst is
0.8kg, continues hydrogenation reaction at pressure 17bar, 250 DEG C of inlet temperature, and the gaseous products of extraction enter layer by condenser 6
Parser obtains aniline crude product.
Continuous-stable operates 3 months device under these conditions.Liquid phase nitro phenenyl concentration is about in its stirred tank reactor
1%, fixed bed adiabatic temperature rises 12 DEG C, and air speed is 0.8/hr (nitrobenzene quality/catalyst quality) to oil in chromatography device in bed
It is mutually crude product sampling analysis, wherein nitrobenzene is 8ppm, the by-products total content such as cyclohexanone, cyclohexylamine of excessive hydrogenation
For 101ppm.
Embodiment 3
Nitrobenzene is sent into stirred tank reactor 4, flow by nitrobenzene delivery pump 1 after the heating of nitrobenzene preheater 3
65kg/hr;Water is sent into stirred tank reactor 4, water flow 55kg/hr by water delivery pump 2;Hydrogen is passed through stirred tank reactor
4, flow 1902mol/hr;Reaction kettle uses the Pt/Pd catalyst of load type active carbon, a concentration of 5wt%.In pressure 17bar, temperature
At 160 DEG C of degree, nitrobenzene, which is reacted with hydrogen in stirred tank reactor, generates aniline and water.
Stirred tank reactor gas phase discharges into fixed bed reactors 5, and the reaction was continued, and the flow of 2kg/hr is pressed in stirred tank
Liquid material is produced, after filter 7 filters out catalyst, is sprayed to after fixed bed bottom end is mixed with gas phase that the reaction was continued, fixation
Using cu-zn-al alloy catalyst (preparation method with reference to patent CN106000408A) in bed, loaded catalyst 0.8kg,
Continue hydrogenation reaction at pressure 17bar, 160 DEG C of inlet temperature, the gaseous products of extraction enter chromatography device by condenser 6 and obtain
Aniline crude product.
Continuous-stable operates 3 months device under these conditions.Liquid phase nitro phenenyl concentration is about in its stirred tank reactor
9%, fixed bed adiabatic temperature rises 94 DEG C, and air speed is 8.1/hr (nitrobenzene quality/catalyst quality) to oil in chromatography device in bed
It is mutually crude product sampling analysis, wherein nitrobenzene is 3ppm, the by-products total content such as cyclohexanone, cyclohexylamine of excessive hydrogenation
For 129ppm.
Comparative example 1
The comparative example is reacted only with above-mentioned stirred tank reactor.
Nitrobenzene is sent into stirred tank reactor 4 by nitrobenzene delivery pump 1 after the heating of nitrobenzene preheater 3, and flow is
1kg/hr, water are sent into stirred tank reactor 4 by water delivery pump 2, and water is sent into stirred tank reactor 4, flow by water delivery pump 2
Amount is 0.85kg/hr;Hydrogen is passed through stirred tank reactor 4, flow 36mol/hr, reaction kettle uses the Pt/ of load type active carbon
Pd catalyst, a concentration of 2wt%.At pressure 17bar, 200 DEG C of temperature, nitrobenzene is reacted with hydrogen in stirred tank reactor
Generate aniline and water.
Continuous-stable operates 3 months device under these conditions.To oil phase, that is, crude product sampling analysis in chromatography device, wherein
Nitrobenzene is 23ppm, and the by-products total content such as cyclohexanone, cyclohexylamine of excessive hydrogenation is 350ppm.
Comparative example 2
The comparative example is reacted only with above-mentioned stirred tank reactor.
Nitrobenzene is sent into stirred tank reactor 4 by nitrobenzene delivery pump 1 after the heating of nitrobenzene preheater 3, and flow is
0.5kg/hr, water are sent into stirred tank reactor 4 by water delivery pump 2, and water is sent into stirred tank reactor 4, water by water delivery pump 2
Flow is 0.42kg/hr;Hydrogen is passed through stirred tank reactor 4, flow 18mol/hr, reaction kettle is using load type active carbon
Pt/Pd catalyst, a concentration of 2wt%.At pressure 17bar, 200 DEG C of temperature, nitrobenzene is with hydrogen in stirred tank reactor
Reaction generates aniline and water.
Continuous-stable operates 3 months device under these conditions.To oil phase, that is, crude product sampling analysis in chromatography device, wherein
Nitrobenzene is 16ppm, and the by-products total content such as cyclohexanone, cyclohexylamine of excessive hydrogenation is 487ppm.
It is can be found that by the comparison of embodiment and comparative example:Comparative example also may be used by increasing the residence time in reaction kettle
To obtain relatively high nitrobenzene conversion rate, but the by-product that the extension of residence time causes nitrobenzene excessive hydrogenation to generate is aobvious
Work increases.Nitro compound high conversion rate in the method for the present invention, while by-product is few, catalyst deactivation rate is extremely low, has
Good industrial prospect.
Claims (10)
1. a kind of nitro compound Hydrogenation passes through stirred tank reactor and fixed bed reaction for the method for amine product, this method
The continuous reaction system of device composition realizes that system includes two stages of reaction:(1) raw material carries out adding hydrogen in stirred tank reactor
Reaction;(2) discharging of stirred tank reactor gas phase continues hydrogenation reaction, while stirred tank reactor into fixed bed reactors
Bottom produces a small amount of liquid phase, also continues hydrogenation reaction into fixed bed reactors after filtering out catalyst.
2. according to the method described in claim 1, it is characterized in that, stirred tank reactor top gas phase produces in continuous reaction system
Object outlet is connected with fixed bed reactors lower part;Stirred tank reactor bottom be arranged liquid phase discharge port, be sequentially connected delivery pump,
Atomizer is arranged in catalyst filter to fixed bed bottom feed inlet, feed inlet upper end;Fixed bed top gas phase discharge port according to
Secondary connection product condenser and chromatography device.
3. method according to claim 1 or 2, which is characterized in that liquid phase nitration in kettle in the reaction process in stage (1)
It closes object concentration and is maintained at 1-10wt%, preferably 3-5wt%.
4. method according to any one of claim 1-3, which is characterized in that stage (1) hydrogen is relative to nitro compound
The overrate of object is 2-20mol%, preferably 5-15mol%.
5. according to the described method of any one of claim 1-4, which is characterized in that the stage (1) using noble metal, nickel, copper,
Zinc, aluminium hydrogenation catalyst, preferably noble metal catalyst, more preferable palladium, platinum catalyst, catalyst concn is 0.2- in reaction kettle
5wt%, preferably 1-2wt%.
6. method according to any one of claims 1-5, which is characterized in that stage (1) reactor bottom produces liquid phase
Amount is the 0.1-2wt% of liquid phase feeding amount.
7. according to the method described in any one of claim 1-6, which is characterized in that stage (1) reactor temperature 160-250
DEG C, preferably 200-220 DEG C.
8. according to the described method of any one of claim 1-7, which is characterized in that the stage (2) is using reaction at this stage
Under the conditions of only make nitro hydrogenation and phenyl ring is not added with the low activity catalyst of hydrogen, preferably Cu-series catalyst, more preferable cu-zn-al alloy
Catalyst.
9. according to the method described in any one of claim 1-8, which is characterized in that stage (2) feeding temperature is 150-220
DEG C, it is preferably consistent with stirred tank reactor drop temperature;Fixed bed reactors pressure 1-20bar.
10. according to the method described in claim 1, the nitro compound be selected from aromatic nitro compound, preferably between/it is right
It is one or more in dinitrobenzene, nitrotoleune, nitrobenzene, 2- meta-xylenes, nitronaphthalene, more preferable nitrobenzene.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810690169.2A CN108623476B (en) | 2018-06-28 | 2018-06-28 | Method for preparing amine products by hydrogenation of nitro compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810690169.2A CN108623476B (en) | 2018-06-28 | 2018-06-28 | Method for preparing amine products by hydrogenation of nitro compounds |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108623476A true CN108623476A (en) | 2018-10-09 |
CN108623476B CN108623476B (en) | 2023-05-30 |
Family
ID=63688535
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810690169.2A Active CN108623476B (en) | 2018-06-28 | 2018-06-28 | Method for preparing amine products by hydrogenation of nitro compounds |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108623476B (en) |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1123790A (en) * | 1994-08-08 | 1996-06-05 | 拜尔公司 | A process for producing aromatic amines |
CN1129212A (en) * | 1994-08-08 | 1996-08-21 | 拜尔公司 | Process for the production of aromatic amines |
CN1470498A (en) * | 2003-07-04 | 2004-01-28 | 石光强 | Method for continuous hydrogenation preparation of 4-amino diphenylamine |
CN1814582A (en) * | 2006-02-24 | 2006-08-09 | 浙江工业大学 | One-step method for preparing N-alkyl aromatic amine from aromatic nitro substance |
CN1861571A (en) * | 2006-06-19 | 2006-11-15 | 常州市佳森化工有限公司 | Tech. of preparing 2,4-diamino methy-phenoxide using 2,4-dinictro methyl phenoxide |
CN101113135A (en) * | 2006-07-29 | 2008-01-30 | 拜尔材料科学股份公司 | Method for producing aromatic amines |
CN101875610A (en) * | 2009-04-29 | 2010-11-03 | 拜尔材料科学股份公司 | Process for preparing aromatic amines |
CN102151525A (en) * | 2011-01-27 | 2011-08-17 | 甘肃银光聚银化工有限公司 | High-efficiency hydrogenation device and dinitrotoluene hydrogenating method |
CN102712568A (en) * | 2010-01-14 | 2012-10-03 | 拜耳知识产权有限责任公司 | Method for producing aromatic amines in the liquid phase |
CN103012160A (en) * | 2012-12-21 | 2013-04-03 | 江苏扬农化工集团有限公司 | Preparation method of o-phenylenediamine |
CN103360265A (en) * | 2012-04-06 | 2013-10-23 | 浙江龙盛化工研究有限公司 | Method for continuous hydrogenation of dinitrobenzene and recycling of reaction heat thereof |
CN106866429A (en) * | 2017-04-10 | 2017-06-20 | 上海迅凯新材料科技有限公司 | Serialization catalytic hydrogenation is produced and catalyst regeneration device and method |
CN108164424A (en) * | 2017-12-29 | 2018-06-15 | 烟台安诺其精细化工有限公司 | The preparation method of 4-ADPA |
-
2018
- 2018-06-28 CN CN201810690169.2A patent/CN108623476B/en active Active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1123790A (en) * | 1994-08-08 | 1996-06-05 | 拜尔公司 | A process for producing aromatic amines |
CN1129212A (en) * | 1994-08-08 | 1996-08-21 | 拜尔公司 | Process for the production of aromatic amines |
CN1470498A (en) * | 2003-07-04 | 2004-01-28 | 石光强 | Method for continuous hydrogenation preparation of 4-amino diphenylamine |
CN1814582A (en) * | 2006-02-24 | 2006-08-09 | 浙江工业大学 | One-step method for preparing N-alkyl aromatic amine from aromatic nitro substance |
CN1861571A (en) * | 2006-06-19 | 2006-11-15 | 常州市佳森化工有限公司 | Tech. of preparing 2,4-diamino methy-phenoxide using 2,4-dinictro methyl phenoxide |
CN101113135A (en) * | 2006-07-29 | 2008-01-30 | 拜尔材料科学股份公司 | Method for producing aromatic amines |
CN101875610A (en) * | 2009-04-29 | 2010-11-03 | 拜尔材料科学股份公司 | Process for preparing aromatic amines |
CN102712568A (en) * | 2010-01-14 | 2012-10-03 | 拜耳知识产权有限责任公司 | Method for producing aromatic amines in the liquid phase |
CN102151525A (en) * | 2011-01-27 | 2011-08-17 | 甘肃银光聚银化工有限公司 | High-efficiency hydrogenation device and dinitrotoluene hydrogenating method |
CN103360265A (en) * | 2012-04-06 | 2013-10-23 | 浙江龙盛化工研究有限公司 | Method for continuous hydrogenation of dinitrobenzene and recycling of reaction heat thereof |
CN103012160A (en) * | 2012-12-21 | 2013-04-03 | 江苏扬农化工集团有限公司 | Preparation method of o-phenylenediamine |
CN106866429A (en) * | 2017-04-10 | 2017-06-20 | 上海迅凯新材料科技有限公司 | Serialization catalytic hydrogenation is produced and catalyst regeneration device and method |
CN108164424A (en) * | 2017-12-29 | 2018-06-15 | 烟台安诺其精细化工有限公司 | The preparation method of 4-ADPA |
Non-Patent Citations (1)
Title |
---|
张超林等: "硝基苯液相催化加氢制苯胺技术进展", 《现代化工》 * |
Also Published As
Publication number | Publication date |
---|---|
CN108623476B (en) | 2023-05-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101410361B (en) | Method of producing lower alcohols from glycerol | |
TWI421234B (en) | Method for producing 2-propanol | |
CN106518608A (en) | A continuous preparing method and apparatus for cyclohexanedimethanol | |
CN101434569A (en) | Method and equipment for preparing caprolactam from cyclohexanone oxime | |
CN101074199B (en) | Method of producing xylylenediamine | |
CN101619025A (en) | Continuous preparation method for n-pentylamine | |
CN107124881B (en) | From the method for phenol production cyclohexanone | |
CN107570146B (en) | Catalyst for directly loading active metal on metal filler | |
CN101891592A (en) | Method for preparing 1,4-butanediol and co-producing tetrahydrofuran and gamma-butyrolactone | |
CN102056879B (en) | Continuous process to produce hexafluoroisopropanol | |
CN108623476A (en) | A kind of nitro compound Hydrogenation for amine product method | |
CN109761819B (en) | Continuous preparation method of N, N-dimethylpropylamine | |
CN109400480B (en) | Method and equipment for preparing methyl nitrite | |
CN109689613B (en) | Process for preparing N-methyl-p-anisidine | |
CN1266113C (en) | Process for production of aromatic amines | |
CN113563213A (en) | Preparation method of 3, 5-diaminobenzoic acid | |
CN101328130B (en) | Preparation of 2-ethoxy ethyl amine | |
JP2013091621A (en) | Reaction process using supercritical water | |
CN106278913A (en) | The method producing ethanolamine | |
CN221062643U (en) | Continuous synthesis system of amino aromatic compound | |
CN112851505B (en) | Process for preparing methyl propionate by continuous gas-phase hydrogenation of methyl acrylate | |
CN114716325B (en) | Method for continuously preparing triethylamine | |
WO2018048319A1 (en) | Method for producing n-methyl-para-phenetidine | |
CN113861122B (en) | Synthesis method for preparing 1H-1,2, 3-triazole by continuous flow | |
CN111138266B (en) | Method and device for preparing acrylic acid or methacrylic acid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |