CN1185207C - Method for continuous hydrogenation preparation of 4-amino diphenylamine - Google Patents
Method for continuous hydrogenation preparation of 4-amino diphenylamine Download PDFInfo
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- CN1185207C CN1185207C CNB031481957A CN03148195A CN1185207C CN 1185207 C CN1185207 C CN 1185207C CN B031481957 A CNB031481957 A CN B031481957A CN 03148195 A CN03148195 A CN 03148195A CN 1185207 C CN1185207 C CN 1185207C
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- Prior art keywords
- hydrogenation
- aminodiphenylamine
- prepares
- catalyzer
- liquid
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 28
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 3
- 239000007788 liquid Substances 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 claims description 7
- XXYMSQQCBUKFHE-UHFFFAOYSA-N 4-nitro-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC1=CC=CC=C1 XXYMSQQCBUKFHE-UHFFFAOYSA-N 0.000 claims description 6
- 239000006148 magnetic separator Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 2
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- -1 4 nitrodiphenyl amines Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a method for preparing 4-amino diphenylamine by continuously hydrogenating condensed liquid obtained from the reaction of nitrobenzene and aniline as raw material, which has the technological process of adopting composite powdery catalysts and solvent and selecting corresponding continuous hydrogenation reaction, namely to adopt the novel technology of circulating catalysts and hydrogen gas and recycling solvent to guarantee continuous hydrogenation reaction under the conditions of high concentration, low temperature and low pressure. As a result, the defects of complicated technical operation, high device investment and low utilization rate of intermittent hydrogenation reaction are overcome, and the defect of high production cost caused by adopting noble metal as catalysts for hydrogenation reducing reaction, etc. is also overcome. The conversion rate of the catalytic hydrogenation in the method of the present invention can reach 100%, and the selectivity is larger than 99%. Simultaneously, the method has the advantages of high product yield, little investment and low cost and is suitable for the industrial scale production of 4-amino diphenylamine.
Description
Technical field
The present invention relates to the preparation method of 4-aminodiphenylamine, be specifically related to select for use a kind of composite powder powder catalyzer and technical process, continuous hydrogenation is that the method for the condensated liquid of raw material prepares the 4-aminodiphenylamine with oil of mirbane and aniline.
Background technology
With oil of mirbane and aniline is raw material, can make 4 nitrodiphenyl amine and 4-nitrosodiphenylamine or/and their salt condensated liquid in the presence of catalyzer.In order to obtain the 4-aminodiphenylamine, can adopt different reductive agent reduction 4 nitrodiphenyl amines and 4-nitrosodiphenylamine or/and their composition, as using iron (Fe) powder, sodium sulfide reducing, but these methods exist a common issue with to be, severe reaction conditions, yield is low, and side reaction is many, and exists a large amount of " three wastes " to pollute; In addition, traditional hydrogenation process at intermittence, because of each stage reactor must be through processes such as pressure testing, displacement, reaction and recovery initial conditions, this troublesome operation of going round and beginning again, not only labour intensity is big, catalyst life is short, and the periodical operation investment is big, plant factor is low, can cause hydrogen loss big in operation, and its hydrogenation equipment is also because of at normal pressure with blocked operation under the pressure condition arranged, can increase the fatigue strength of hydrogenation reactor, thereby reduce the life-span of reactor, what influence was produced carries out smoothly, so be difficult to realize automatic production.In addition, the method of existing employing hydrogen hydrogenating reduction, the catalyzer raw material that it adopted are expensive palladium (Pd), platinum (Pt), rhodium noble dilute metals such as (Rh), this rareness of not only originating, and the antitoxin poor performance of catalyzer, production cost height (referring to CN1307556A).
Summary of the invention
The technical issues that need to address of the present invention are to select the technical process of appropriate catalyst and reaction, control hydrogenation processing condition and relevant device etc., and continuous hydrogenation prepares the 4-aminodiphenylamine.
The present invention selects a kind of composite powder powder catalyzer, solvent and technical process for use, by the circulation of hydrogen and catalyzer, hydrogenation is carried out continuously.
Below describe particular content of the present invention in detail:
The technical process of hydrogenation of the present invention is: with oil of mirbane and aniline is the condensated liquid that generates after condensation reaction of raw material and hydrogenation solvent and through the composite powder powder catalyzer of sedimentation and magnetic Separation and Recovery, successively enter one-level by the solid-liquid e Foerderanlage, secondary or multistage hydrogenation reactor, hydrogen enters from reactor bottom by the form of hydrogen recycle machine with bubbling, the control certain condition carries out hydrogenation, generation contains the hydride of 4-aminodiphenylamine, separate with magnetic separator through settling vessel being hydrogenated the composite powder powder catalyzer that liquid carries secretly, make catalyzer pass through the solid-liquid e Foerderanlage, reenter the A reactor recycled, obtain containing the hydride of 4-aminodiphenylamine simultaneously.For hydrogenation is normally carried out continuously, in the reaction process, need to replenish the fresh composite powder powder catalyzer of interpolation.
In the hydrogenation of the present invention, hydrogenation solvent can be a recycled.
In the continuous hydrogenation process, because of the hydrogen recycle machine that cycles through of hydrogen enters reactor with the form of bubbling, so just increased the effect of gas-liquid mass transfer, improved the solubleness of hydrogen in liquid, make in the solid, liquid, gas phase reaction process, hydrogen gas bubbles is littler, wider in the distribution of liquid phase, has overcome hydrogen and has entered reactor from top, the limitation that just relies on the frictional belt on the surface of liquid material to contact with gas.
In series connection complete mixing flow formula reactor, the successive input and output material must be taken a part of powder catalyst out of, has not only increased the consumption of catalyzer, has increased production cost, in case and the ingress of air of taking out of of catalyzer burn easily, produce major safety risks.For this reason, the present invention has designed a kind of telescopic settling vessel, make the powder catalyst major part in this sedimentation, but in full series connection mixed-flow reactor, when solid, liquid, gas three contact, still have sub-fraction powder catalyst shape to break, it is big that the order number becomes, be difficult to sedimentation, along with the condensated liquid material runs off together.In order to reclaim this part catalyzer, the present invention adopts magnetic separator, make granules of catalyst with magnetic, separated catch to return apply mechanically, through Venturi-type solid-liquid e Foerderanlage catalyzer is turned back in the A reactor, thereby realized the circulation of catalyzer and apply mechanically, and the material that contains the 4-aminodiphenylamine is not because of having magnetic, pass through magnetic separator smoothly, thereby with the two smooth separation.
Composite powder powder catalyzer of the present invention, its composition be nickel (Ni), aluminium (Al) and " other metal or nonmetal " (A), wherein A is a kind of among Fe, Cu, Cr, Co, Mn, Mo, B, the P, each components contents of catalyzer is, nickel (Ni) content is 25-99.9 (weight %), aluminium (Al) and " other metal or nonmetal " (A) content are 0.1-75 (weight %), and the order number of catalyzer is the 40-300 order.
In the continuous hydrogenation process, the circulation of composite powder powder catalyzer of the present invention is to use the no pump circulation that reinforced power carries out by a kind of solid-liquid e Foerderanlage of Venturi-type.
The hydrogenation hydrogenation of 4-nitrosodiphenylamine and 4 nitrodiphenyl amine is the solid, liquid, gas phase reaction, and 4 nitrodiphenyl amine is reduced to the 4-nitrosodiphenylamine earlier, is reduced to azanol again, is reduced to the 4-aminodiphenylamine at last.Reactant through interior external diffusion, absorption in catalyst active center, carry out surface reaction, resultant and take off steps such as absorption and inside and outside diffusion in catalyst active center and obtain product, mass transfer is the controlled step of reaction.Hydrogenation of the present invention has kept higher vapour-liquid ratio, and gas promptly refers to hydrogen, and liquid comprises solvent and condensated liquid, and it is than being 10: 1-1500: 1 (volume), and solid-to-liquid ratio is 0.5: 100-6: 100 (weight), solid promptly are meant composite powder powder catalyzer.This helps to eliminate the influence of external diffusion, guarantees mass transfer effect, and hydrogenation is carried out under high density, low pressure, low temperature conditions continuously.
The present invention adopts alcohol and/or water to make hydrogenation solvent, alcohols particular methanol or ethanol or Virahol according to the characteristics of catalyzer.Solvent: condensated liquid=1: 1 0-5: 10 (weight %) add solvent and can improve the solid, liquid, gas mass transfer effect, improve catalyst activity, shorten the reaction times.
Composite powder powder catalyzer of the present invention is used for hydrogenation hydrogenating reduction condensated liquid, its temperature of reactor be 50-100 (℃), pressure is 0.2-3.0 (MPa), by one or more levels reactors in series, the time of hydrogenation is 2-7 hour, adopts magnetic separator and settling vessel to reclaim composite powder powder catalyzer.
Continuous hydrogenation hydrogenation of the present invention is produced the method for 4-aminodiphenylamine, by composite powder powder catalyzer and solvent, hydrogen recycle and catalyst recirculation and apply mechanically, overcome intermittently hydrogenation investment greatly, plant factor is low, complicated operation, catalyst life is short, system intermittently contact the unsafe factor that brings and hydrogen to shortcomings such as environment must interruption discharge with air, solved in a high density liquid phase continuous hydrogenation and the difficult problem that is used for reducing catalyzer ton unit consumption of product by cover, make the transformation efficiency of catalytic hydrogenation can reach 100%, selectivity is greater than 99%, yield is greater than 99%, the powder catalyst unit consumption is less than 0.6%, thereby but the continuous hydrogenation condensated liquid prepares the 4-aminodiphenylamine.
Description of drawings
Accompanying drawing is the process flow sheet that continuous hydrogenation prepares the 4-aminodiphenylamine
1-applies mechanically the composite powder powder catalyzer that solvent 2-applies mechanically
3-hydrogen returns the hydrogen of circulator 4-from circulator
The composite powder powder catalyzer that 5-hydride 6-is fresh
Embodiment
Embodiment 1
The resistance to air loss of elder generation's inspection units, the system leak rate performs the preparation work before feeding intake then less than 5% after requiring to use the nitrogen pressure testing, completes bed material, uses hydrogen exchange nitrogen, and pressurising is started circulator and is kept the flow of recycle hydrogen at 6 meters to 1.3MPa
3(mark side)/hour, hydrogen enters hydrogenation reactor by circulator with the form of bubbling, the mass transfer effect of gas-liquid during with augmenting response, the flow of the condensated liquid behind oil of mirbane and the aniline reaction is 200 kilograms/hour, the flow of methyl alcohol is 60 kilograms/hour, mix back 4-nitrosodiphenylamine content 15.1 (weight %), 4 nitrodiphenyl amine content 2.5 (weight %) enters the one-level hydrogenation reactor, and reactor has magnetic seal and stirs, the cooling heating system, add composite powder powder catalyzer simultaneously, the temperature 75-80 of maintenance reaction (℃), pressure 1.3MPa, the residence time is 5 hours, solid-to-liquid ratio 3: 100 (weight), the reduced liquid of system overflows to the second order reaction still from the first order reaction still, the third order reaction still, overflow to subsider, under the effect of magnetic separator, the maximum possible recovery catalyzer, subsider bottom contain the bigger solidliquid mixture of solid catalyst concentration, through the solid-liquid e Foerderanlage, come back to reactor, realized applying mechanically circulation the circulation of hydrogen like this at the continuous production catalyzer.Reduced liquid detects through high performance liquid chromatography, does not contain 4 nitrodiphenyl amine, the 4-nitrosodiphenylamine, and the transformation efficiency of catalytic hydrogenation can reach 100%, and selectivity is greater than 99%, and yield is 99.1%.
Claims (11)
1, a kind of hydrogenation prepares the method for 4-aminodiphenylamine, the hydrogenant raw material is the 4 nitrodiphenyl amine that makes of oil of mirbane and aniline condensation reaction and the condensated liquid of 4-nitrosodiphenylamine and/or their salt, it is characterized in that selecting for use the composite powder powder catalyzer of forming by nickel, aluminium and " other metal or nonmetal " A, with alcohols and/or water is solvent, circulation by hydrogen and catalyzer, hydrogenation carries out continuously, and wherein said " other metal or nonmetal " A is a kind of among Fe, Cu, Cr, Co, Mn, Mo, B, the P.
2, hydrogenation according to claim 1 prepares the method for 4-aminodiphenylamine, it is characterized in that in the composite powder powder catalyzer, the weight percentage of nickel is 25%-99.9%, and the weight percentage of aluminium and " other metal or nonmetal " A is 0.1%-75%.
3, hydrogenation according to claim 1 prepares the method for 4-aminodiphenylamine, and the circulation that it is characterized in that hydrogen is to enter hydrogenation reactor by the hydrogen recycle machine in the bubbling mode.
4, hydrogenation according to claim 1 prepares the method for 4-aminodiphenylamine, it is characterized in that catalyzer passes through a kind of solid-liquid e Foerderanlage of Venturi-type, and uses reinforced power and enter hydrogenation reactor.
5, hydrogenation according to claim 1 prepares the method for 4-aminodiphenylamine, it is characterized in that magnetic separator and settling vessel are adopted in the recovery of catalyzer.
6, hydrogenation according to claim 1 prepares the method for 4-aminodiphenylamine, it is characterized in that alcohols is methyl alcohol or ethanol or Virahol in the solvent that hydrogenation uses.
7, hydrogenation according to claim 1 prepares the method for 4-aminodiphenylamine, it is characterized in that gas-liquid volume ratio is 10: 1-1500: 1, the solid-liquid weight ratio is 0.5: 100-6: 100, wherein gas is meant hydrogen, liquid is meant solvent and condensated liquid, and solid is meant composite powder powder catalyzer.
8, hydrogenation according to claim 1 prepares the method for 4-aminodiphenylamine, and the weight ratio that it is characterized in that solvent and condensated liquid is 1: 10-5: 10.
9, hydrogenation according to claim 1 prepares the method for 4-aminodiphenylamine, and the temperature that it is characterized in that hydrogenation is 50-100 ℃.
10, hydrogenation according to claim 1 prepares the method for 4-aminodiphenylamine, and the pressure that it is characterized in that the reactor of hydro-reduction is 0.2-3.0MPa.
11, hydrogenation according to claim 1 prepares the method for 4-aminodiphenylamine, it is characterized in that the hydrogenation time is 2-7 hour.
Priority Applications (31)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031481957A CN1185207C (en) | 2003-07-04 | 2003-07-04 | Method for continuous hydrogenation preparation of 4-amino diphenylamine |
| BRPI0412101-5A BRPI0412101A (en) | 2003-07-04 | 2004-07-02 | process for the preparation of 4-aminodiphenylamine |
| ES04738332T ES2373720T3 (en) | 2003-07-04 | 2004-07-02 | METHOD FOR THE PRODUCTION OF 4-AMINODYPHENYLAMINE. |
| JP2006500463A JP4500302B2 (en) | 2003-07-04 | 2004-07-02 | Method for producing 4-aminodiphenylamine |
| CA2531074A CA2531074C (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| PL04738332T PL1645555T3 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| EA200501647A EA009395B1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| CA2515238A CA2515238C (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| AT04738332T ATE526305T1 (en) | 2003-07-04 | 2004-07-02 | METHOD FOR PRODUCING 4-AMINODIPHENYLAMINE |
| DE602004010234T DE602004010234T2 (en) | 2003-07-04 | 2004-07-02 | PROCESS FOR THE PREPARATION OF 4-AMINODIPHENYLAMINE |
| MXPA05013788A MXPA05013788A (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine. |
| KR1020040051541A KR100612922B1 (en) | 2003-07-04 | 2004-07-02 | A process for producing 4-aminodiphenylamine |
| ES04738331T ES2298762T3 (en) | 2003-07-04 | 2004-07-02 | PROCESS TO PREPARE 4-AMINODYPHENYLAMINE. |
| EP04738331A EP1591438B1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| EP04738332A EP1645555B1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| PCT/CN2004/000733 WO2005003078A1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| PCT/CN2004/000734 WO2005003079A1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| US10/883,042 US7084302B2 (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| US10/882,677 US7176333B2 (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| PT04738332T PT1645555E (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| JP2006517937A JP4546958B2 (en) | 2003-07-04 | 2004-07-02 | Method for producing 4-aminodiphenylamine |
| EA200600052A EA009396B1 (en) | 2003-07-04 | 2004-07-02 | A method for producing 4-aminodiphenylamine |
| KR1020040051932A KR100612923B1 (en) | 2003-07-04 | 2004-07-05 | A process for preparing 4-aminodiphenylamine |
| US11/477,954 US7235694B2 (en) | 2003-07-04 | 2006-06-30 | Process for preparing 4-aminodiphenylamine |
| US11/757,277 US20080039657A1 (en) | 2003-07-04 | 2007-06-01 | Process for preparing 4-aminodiphenylamine |
| US11/759,901 US20070227675A1 (en) | 2003-07-04 | 2007-06-07 | Process for preparing 4-aminodiphenylamine |
| US11/759,897 US8293673B2 (en) | 2003-07-04 | 2007-06-07 | Process for preparing 4-aminodiphenylamine |
| US12/195,371 US7989662B2 (en) | 2003-07-04 | 2008-08-20 | Process for preparing 4-aminodiphenylamine |
| US12/900,459 US8486223B2 (en) | 2003-07-04 | 2010-10-07 | Falling film evaporator |
| US13/104,900 US8686188B2 (en) | 2003-07-04 | 2011-05-10 | Process for preparing 4-aminodiphenylamine |
| US13/620,588 US9029603B2 (en) | 2003-07-04 | 2012-09-14 | Process for preparing alkylated p-phenylenediamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031481957A CN1185207C (en) | 2003-07-04 | 2003-07-04 | Method for continuous hydrogenation preparation of 4-amino diphenylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1470498A CN1470498A (en) | 2004-01-28 |
| CN1185207C true CN1185207C (en) | 2005-01-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031481957A Expired - Lifetime CN1185207C (en) | 2003-07-04 | 2003-07-04 | Method for continuous hydrogenation preparation of 4-amino diphenylamine |
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| Country | Link |
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| CN (1) | CN1185207C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104741145B (en) * | 2013-12-25 | 2017-02-08 | 浙江衢州万能达科技有限公司 | Preparation method of hydrogenation catalyst for m-(trifluoromethyl) aniline |
| CN107118108B (en) * | 2017-06-06 | 2018-07-20 | 青岛科技大学 | A kind of catalytic hydrogenation method of aniline-nitrobenzene condensation liquid |
| CN107138101A (en) * | 2017-06-27 | 2017-09-08 | 查都（上海）科技有限公司 | A kind of system of acetylene and formaldehyde deep reaction |
| CN108623476B (en) * | 2018-06-28 | 2023-05-30 | 万华化学集团股份有限公司 | Method for preparing amine products by hydrogenation of nitro compounds |
| CN109485574A (en) * | 2018-11-22 | 2019-03-19 | 湖南湘硕化工有限公司 | A kind of preparation method of 4-ADPA |
-
2003
- 2003-07-04 CN CNB031481957A patent/CN1185207C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1470498A (en) | 2004-01-28 |
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