CN1202073C - method for preparing 4-aminodiphenylamine - Google Patents
method for preparing 4-aminodiphenylamine Download PDFInfo
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- CN1202073C CN1202073C CN 03148199 CN03148199A CN1202073C CN 1202073 C CN1202073 C CN 1202073C CN 03148199 CN03148199 CN 03148199 CN 03148199 A CN03148199 A CN 03148199A CN 1202073 C CN1202073 C CN 1202073C
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- Prior art keywords
- aniline
- aminodiphenylamine
- mirbane
- oil
- hydrogenation
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- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 48
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 238000009833 condensation Methods 0.000 claims abstract description 14
- 230000005494 condensation Effects 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000006482 condensation reaction Methods 0.000 claims abstract description 11
- 238000007670 refining Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000000605 extraction Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 150000004678 hydrides Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 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
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 241000282326 Felis catus Species 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 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 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011552 falling film Substances 0.000 description 6
- OIJHFHYPXWSVPF-UHFFFAOYSA-N para-Nitrosodiphenylamine Chemical compound C1=CC(N=O)=CC=C1NC1=CC=CC=C1 OIJHFHYPXWSVPF-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 239000006200 vaporizer Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000006148 magnetic separator Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000000998 batch distillation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 2
- 238000004845 hydriding Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response 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
- 239000002893 slag Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The present invention discloses a method for preparing 4-aminodiphenylamine from nitrobenzene and aniline as raw material. A composite base catalyst and a composite powdery catalyst corresponding to condensation reaction and hydrogenation reaction are respectively selected. The whole technology orderly forms a circulating technological process from condensation, hydrogenation, separation, recovery and reuse of the composite base catalyst, recovery and reuse of the regenerated composite powdery catalyst, separation, recovery and reuse of hydrogenation solvent and aniline, and refining. The preparing method is continuous. The two selected composite catalysts have the advantages of low price, high catalytic activity, mild reaction condition and few byproducts. The whole preparing process is continuous, and the method is suitable for industrial scale production. The content of the prepared 4-aminodiphenylamine is higher than 99 wt%, and the yield of industrial scale production is higher than 92%.
Description
Technical field
The present invention relates to prepare the method for 4-aminodiphenylamine, being specifically related to oil of mirbane, aniline is raw material, adopts two kinds of composite catalysts and cyclical operation technical process, prepares the method for 4-aminodiphenylamine continuously.
Background technology
The 4-aminodiphenylamine is the intermediates of important antioxidants and stablizer, it is important chemical product in rubber industry and the polymer industry, according to the difference of using raw material, at present, the method of producing the 4-aminodiphenylamine has, and (1) aniline process is a raw material with p-Nitrophenyl chloride and aniline, reaction generates 4 nitrodiphenyl amine under catalyst action, is the 4-aminodiphenylamine with sodium sulfide reducing then.(2) formylaniline method is that raw material reaction generates formylaniline with formic acid and aniline, reacts in the presence of acid binding agent with p-Nitrophenyl chloride to generate 4 nitrodiphenyl amine again, prepares the 4-aminodiphenylamine with sodium sulfide reducing then.(3) pentanoic method, it promptly is raw material with the pentanoic, in organic solvent, carry out nitrosification with nitrite, obtain N nitrosodiphenyl amine, again with anhydrous hydrogen chloride reset 4-nitrosodiphenylamine hydrochloride, with in the alkali and generate the 4-nitrosodiphenylamine, get the 4-aminodiphenylamine with sodium sulfide reducing at last.Although these method raw material differences are all used traditional Sodium Sulphide to make reductive agent and produced the 4-aminodiphenylamine, the shortcoming of these reactions is severe reaction conditions, complicated operation, and the energy consumption height, yield is low, and cost is high and produce contaminate environment etc. with " three wastes ".
In recent years, produce raw material that the 4-aminodiphenylamine adopts and mostly be oil of mirbane or oil of mirbane and aniline or nitrosobenzene and carry out condensation reaction, then with hydrogen hydrogenation make (referring to publication number CN1209430A, CN1235153A, CN1193010A, CN1307556A).These methods are that the mixture with the above raw material of hydrogen hydrogenation prepares the 4-aminodiphenylamine in the presence of catalyzer, but all there are some common shortcomings: the one,, selected catalyzer costs an arm and a leg, applicable industry scale production meeting causes production cost too high, and comparing with present production technique does not have advantage.For example, the noble dilute metal palladium metal (Pd) that tetraalkylammonium hydroxide that condensation reaction is used and hydrogenation adopt, platinum (Pt), rhodium (Rh) etc., raw material sources are few, and price is extremely expensive.The 2nd,, operate more loaded down with trivial detailsly, be unfavorable for serialization, industrial scale is restricted.The 3rd,, product purity is not high.
Summary of the invention
The technical issues that need to address of the present invention are to select to be used for catalyzer and technical process that is suitable for industrial-scale production of condensation, hydrogenation, inexpensive and superior performance, prepare the 4-aminodiphenylamine continuously.
The present invention is by adopting compound alkaline catalysts and composite powder powder catalyzer respectively in condensation and hydriding process, and carry out condensation, hydrogenation, separation I successively, separate the cyclical operation flow process of II and five operations such as refining, prepare the 4-aminodiphenylamine continuously.
Detailed content of the present invention is as follows:
In the technical process of the present invention, " separate I " be meant " separate, reclaim with apply mechanically regeneration after composite powder powder catalyzer and separate, reclaim and apply mechanically compound alkaline catalysts ", " separating II " is meant " separate, reclaim and apply mechanically hydrogenation solvent and aniline ".
Technical process of the present invention is, with oil of mirbane, aniline and compound alkaline catalysts by a certain percentage, enters the condensation operation continuously by volume pump, and reaction generates and contains 4 nitrodiphenyl amine and 4-nitrosodiphenylamine or/and the condensated liquid of their salt.Condensated liquid and hydrogenation solvent enter hydrogenation process by a certain percentage continuously, under the effect of composite powder powder catalyzer and hydrogen reaction, obtain containing the hydride of 4-aminodiphenylamine.Enter and separate the I operation, hydride filters and obtains composite powder powder catalyzer, applies mechanically back hydrogenation process after the regeneration, and after composite powder powder catalyst separating, hydride is through extraction, concentrated, and base of evaporator obtains compound alkaline catalysts, applying mechanically retraction and closing operation.The vaporizer top is obtained organic phase after hydrogenation solvent and water mixed liquid and the extraction to be entered respectively and separates the II operation, be that the mixed solution of rectifying hydrogenation solvent and water obtains hydrogenation solvent and applies mechanically back hydrogenation process, the organic phase after the extraction obtains aniline and applies mechanically retraction and close operation.The organic phase that contains 4-aminodiphenylamine crude product of having separated most of aniline is entered refining step, and cutting out partial aniline is applied mechanically retraction and is closed operation, and the finished product of gained is the 4-aminodiphenylamine, and whole process flow is carried out continuously.
The operational process of craft of each operation is as follows:
The operation of condensation reaction is, by volume pump oil of mirbane, aniline and compound alkaline catalysts entered the forced heat-exchanging device in proportion continuously and dewaters, and reaction, water vapour is through being condensed into water; Condensated liquid in the forced heat-exchanging device is squeezed into A reactor from its top, continues dehydration, reaction.Then, the condensation recycle pump by reactor bottom returns condensated liquid to the forced heat-exchanging device again, and material constitutes the local circulation system of condensation reaction of the present invention through circulation constantly like this.Material constantly dewaters, and reaction is along with increasing of condensated liquid in the A reactor, upflow tube by this reactor side enters second reactor and staged reactor, dewater, reaction generates at last and contains 4 nitrodiphenyl amine and 4-nitrosodiphenylamine or/and the condensated liquid of their salt.
Oil of mirbane is 1 with the ratio of aniline in the condensation reaction: 1-1: 15 (moles), preferably than being 1: 4-1: 10 (moles), temperature of reaction be 20-150 (℃), preferred 50-90 (℃), control reaction temperature is not higher than 90 ℃, make the compound alkaline catalysts rate of decomposition of condensation course less than 0.5%, reaction pressure (absolute pressure) is 0.005-0.1 (MPa), the reaction times of material in whole reactor be 3.5-6 (hour).
The aqueous solution that the compound alkaline catalysts of condensation reaction is made up of tetraalkylammonium hydroxide, alkali metal hydroxide or its oxide compound and tetraalkylammonium salt, wherein tetraalkylammonium hydroxide, alkali metal hydroxide and tetraalkylammonium salt three concentration summation are 15-50 (weight %), be preferably 25-38 (weight %), the ratio of tetraalkylammonium hydroxide, alkali metal hydroxide and tetraalkylammonium salt is (2-9): (0.5-3): (0.5-3) (mole).If adopt alkalimetal oxide, then its consumption in catalyzer can be converted by corresponding oxyhydroxide and draw.The ratio of hydroxide ion and oil of mirbane is 1 in the compound alkaline catalysts: 4-4: 1 (mole).
The preparation method of the compound alkaline catalysts that condensation reaction is adopted is, with tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt is (2-9) in molar ratio: (0.5-3): (0.5-3), be added in certain water gaging controlled temperature, stir, promptly get this compound alkaline catalysts.If adopt alkalimetal oxide, then its consumption in catalyzer can be converted by corresponding oxyhydroxide and draw.
The hydrogenation operation is, successively enter one-level with condensated liquid and hydrogenation solvent with through the composite powder powder catalyzer of sedimentation and magnetic Separation and Recovery 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 apply mechanically back 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 continuous hydrogenation process, composite powder powder catalyzer is by sedimentation, and magnetic separator reclaims, and circulates by Venturi-type solid-liquid e Foerderanlage, and the circulation of hydrogen adopts the form of bubbling to enter reactor.Whole hydriding process takes continuously feeding, the placed in-line complete mixing flow mode of staged reactor to carry out.Hydrogenation solvent can be a recycled.
In the hydrogenation of the present invention, the hydrogenation temperature be 50-100 (℃), pressure is 0.2-3.0 (MPa), the reaction times is 2-7 hour, vapour-liquid ratio is 10: 1-1500: 1 (volume), solid-to-liquid ratio are 0.5: 100-6: 100 (weight).Gas promptly refers to hydrogen, and liquid comprises solvent and condensated liquid, and solid is meant composite powder powder catalyzer.
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; Consisting of of catalyzer, nickel (Ni) content is 25-99.9 (weight %), and 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.
Composite powder powder Preparation of catalysts method of the present invention is, gets a certain amount of nickel powder, and aluminium powder and " other metal or nonmetal " are (A), fusion under the condition of high temperature, pulverize powdered after the discharging, order is counted the 40-300 order, makes with the hydroxide aqueous solution processing under certain temperature and concentration.
In 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.
Among the present invention, hydrogenation adopts alcohols or/and water is made hydrogenation solvent, alcohols particular methanol or ethanol or Virahol according to the characteristics of catalyzer.Solvent: condensated liquid=1: 10-5: 10 (weight).Hydrogenation solvent is pure time-like, need separate and recycled.When hydrogenation solvent was water, the water after the extraction only need concentrate and promptly get the catalyzer that contains the hydroxide tetra-allkylammonium.
The operation of separating I, II is, hydride enters and separates the I operation, obtain composite powder powder catalyzer after the filtration, apply mechanically back hydrogenation process after the regeneration, at extraction agent and helping under the effect of extraction agent, obtain organic phase and water, water is imitated or multiple-effect concentrates carrying out one, obtain containing the catalyzer of hydroxide tetra-allkylammonium, apply mechanically retraction and close operation.
Separating the I operation is, with water is extraction agent, the ratio of it and hydride is 0.5: 1-5: 1 (volume), preferred proportion is 0.8: 1-1.2: 1 (volume), with the polyethers organism for helping extraction agent, preferred polyglycol ether, polypropylene glycol ether, fatty alcohol-polyoxyethylene ether, polyethylene oxide dimethyl, the ratio of its consumption and extraction agent water is 0.01: 1-0.05: 1 (volume).The pressure (absolute pressure) of extraction is 0.005-0.1 (MPa).The extraction temperature be 0-80 (℃), extracted time 2-5 hour.After the discharging, the upper strata is a water, contains hydrogenation solvent and the compound alkaline catalysts that contains the hydroxide tetra-allkylammonium.Organic phase mainly contains aniline and 4-aminodiphenylamine and a small amount of organic impurity thereof.
Concentrate and adopt one to imitate or the multiple-effect concentrating unit.Being used for spissated heating agent is water, the secondary steam of water vapour or last effect, its temperature be 60-150 (℃).Spissated pressure (absolute pressure) is 0.005-0.1 (MPa).The spissated time is 2-60 (second).
Separating the II operation is, help stream falling-film evaporator top to obtain the water of hydrogenation solvent and water mixed liquid the gas and extract after organic phase enter and separate II, hydrogenation solvent and water mixed liquid obtain hydrogenation solvent through rectifying, organic phase obtains aniline through evaporator evaporation, when hydrogenation solvent is water, water after the extraction only need concentrate and promptly get the catalyzer that contains the hydroxide tetra-allkylammonium, need not to obtain hydrogenation solvent by rectifying.
The working pressure that vaporizer evaporates (absolute pressure) is 0.005-0.1Mpa, and the temperature of evaporated liquor is 120-320 ℃, and gas phase temperature is 60-190 ℃.
Refining step is, in separating the II operation with the isolating organic phase of most of aniline in, contain 4-aminodiphenylamine, aniline, nitrogen benzide and azophenlyene etc., adopt three tower continuous rectifications and batch fractionating to make with extra care.Feed liquid is gone in No. 1 rectifying tower by pump delivery, cat head discharging aniline, azophenlyene and nitrogen benzide, the discharging of tower still is a crude product 4-aminodiphenylamine, the cat head discharging of No. 1 rectifying tower enters in No. 3 rectifying tower, No. 3 the rectifying tower cat head steams aniline, its content is 99%, can directly apply mechanically retraction and close operation, remaining azophenlyene of tower still and nitrogen benzide.No. 1 rectifying tower tower bottoms is by pump delivery to 2 tower, No. 2 the rectifying tower cat head distills out finished product 4-aminodiphenylamine, tower still feed liquid runs up to a certain amount of, enter the batch still distillation, distill out remaining a spot of 4-aminodiphenylamine in the feed liquid, eject material from still and return rectifying tower No. 2, other material slag is emitted at the bottom of by still.
Process for refining of the present invention, the vacuum tightness of its No. 1 rectifying tower are 0.09-0.098 (MPa), and reflux ratio is 2: 1-10: 1, tower top temperature be 80-130 (℃), tower still temperature be 260-290 (℃); The vacuum tightness of No. 2 rectifying tower is 0.09-0.098 (MPa), and reflux ratio is 1: 0.5-1: 4, tower top temperature be 140-190 (℃), tower still temperature be 260-300 (℃); The vacuum tightness of No. 3 rectifying tower is 0.09-0.098 (MPa), and reflux ratio is 1: 0.5-1: 2, tower top temperature be 80-120 (℃), tower still temperature be 120-170 (℃).The tower still temperature of No. 2 rectifying tower is relatively low, reduced the coking degree of 4-aminodiphenylamine, the 4-aminodiphenylamine that accounts for total amount 96% has separated at the cat head of No. 2 rectifying tower of relatively low tower still temperature and has made, thereby the amount of carrying out 4-aminodiphenylamine in the feed liquid of batch distillation significantly reduces.The batch still temperature be 280-330 (℃), batch distillation top temperature be 235-250 (℃), vacuum tightness is 0.09-0.098 (MPa).
The method for preparing the 4-aminodiphenylamine of the present invention, with oil of mirbane and aniline is raw material, successively through condensation, hydrogenation, separation I (be Separation and Recovery and apply mechanically regeneration after composite powder powder catalyzer, and Separation and Recovery and apply mechanically compound alkaline catalysts), separate II (being that Separation and Recovery is applied mechanically hydrogenation solvent and aniline), refining step, selected compound alkaline catalysts and composite powder powder catalyzer, cheap, production cost is low, the catalytic activity height; Whole process of preparation is continuous, is suitable for industrial-scale production, has selected to reclaim compound alkaline catalysts after the hydrogenation, only needs water as extraction agent, adds a spot of extraction agent that helps again, promptly separable compound alkaline catalysts; The hydrogenation temperature is lower, the reaction conditions gentleness, and by product is few, transformation efficiency and selectivity height; Labour intensity is low, does not produce corrosive liquid, has alleviated the pollution to environment.The content of 4-aminodiphenylamine can be higher than 99 (weight %), the technological process of whole industrial-scale production, and yield can be higher than 92%.
Description of drawings
Accompanying drawing is the process flow sheet for preparing the method for 4-aminodiphenylamine
Reference numeral
1---composite powder powder catalyzer
2---hydrogenation solvent
3---the compound alkaline catalysts of recovery set
4---the composite powder powder catalyzer of recovery set after the regeneration
5---the recovery set hydrogenation solvent
6---recovery set aniline
Embodiment
Embodiment 1
Open composite catalyst simultaneously, aniline and oil of mirbane transferpump, regulate flow to 150 kilograms/hour of aniline, 30 kilograms/hour in oil of mirbane, compound alkaline catalysts double centner/hour, enter continuously in the forced heat-exchanging device, the heating agent of forced heat-exchanging device adopts alcohol steam, condensated liquid in the forced heat-exchanging device is squeezed into A reactor from its top, continue dehydration, reaction, open A reactor bottom valve and condensation recycle pump then, regulate condensation circulating-pump outlet valve, material is turned back in the forced heat-exchanging device, form the local circulation system, material constantly circulates like this, dehydration, reaction.75 ℃ of control reaction temperature, pressure (absolute pressure) 0.008MPa, the Control Circulation flow quantity is at 2 meters
3/ hour.Along with raw material constantly enters, material in the A reactor constantly increases, when treating that material in the A reactor rises to A reactor to the pipe connecting of second reactor, the material overflow is to second reactor, in second reactor dewater more fully, condensation reaction.The total residence time of control material in reactor 5 hours, material back by analysis detect less than oil of mirbane.
Use hydrogen exchange nitrogen, 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 210 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, the hydro-reduction 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.Hydro-reduction liquid detects through high performance liquid chromatography, does not contain 4 nitrodiphenyl amine, the 4-nitrosodiphenylamine.
Hydro-reduction liquid is through sedimentation, magnetic reclaims and filtered and recycled, composite powder powder hydrogenation catalyst cover is used the one-level hydrogenation reactor, no solid reduction liquid is entered continuously the top of extraction tower with 260 liters/hour flow with volume pump, extraction agent water helps the extraction agent polyglycol ether to enter the bottom of extraction tower continuously with 3 liters of/hour flows with 260 liters of/hour identical flows simultaneously.After the extraction, obtain water, obtain organic phase at the bottom of the tower from cat head.The extraction time is 3 hours, and extracting pressure is a normal pressure, and methyl alcohol in the reduced liquid and condensation composite catalyst all are extracted into aqueous phase by water, and the water amount that obtains is 344 liters/hour, and organic phasor is 176 liters/hour.
Be preheating to 80 ℃ water with volume pump with 344 liters/hour flow, enter gas and help stream falling-film evaporator top, gas helps stream falling-film evaporator shell side to heat 10 seconds residence time in vaporizer of material with 120 ℃ of water vapors.The shell and tube two that one effect concentrated solution enters under the 0.01Mpa pressure (absolute pressure) is imitated falling-film evaporators, about 10 seconds of the residence time of material in vaporizer, from two imitate that falling-film evaporators come out vapour-liquid composition temperature be 80-95 ℃, then after two effect vapour liquid separators separate, the compound alkaline catalysts rate of recovery that whole enrichment process contains the hydroxide tetra-allkylammonium can reach 99.7%,, compound alkaline catalysts is applied mechanically retraction closes operation.
Gas phase after falling-film evaporator separates, after condensation, obtain containing the methanol-water solution of about 28 (the weight %) of methyl alcohol, after entering rectifying tower continuously and separate with pump, cat head obtains the methyl alcohol greater than 99 (weight %), the tower still is a water, surveys tower still water with gas-chromatography, and methanol content is less than 0.3 (weight %).The organic phase that extracting and separating is obtained, send into shell and tube climbing-film evaporator separating most aniline, the working pressure of climbing-film evaporator (absolute pressure) is 0.01Mpa, shell side is with 180 ℃ of steam heating, obtain 75-105 ℃ gas phase and 160 ℃ liquid phase through the separation of climbing-film evaporator top vapour liquid separator, detect condensed gaseous phase materials, record aniline content and reach 99 (weight %) with chromatogram, most of aniline steams in this operation, and the aniline that steams is applied mechanically retraction and closed operation participation reaction.The crude product of liquid phase material 4-aminodiphenylamine is 78.1% for containing the 4-aminodiphenylamine, aniline 20.1%, and remainder is other organic impuritys.
The crude product that contains the 4-aminodiphenylamine that will several covers after above-mentioned same treatment be merged into (contains 4-aminodiphenylamine 78.1%, aniline 20.1%, nitrogen benzide 1.1%, azophenlyene 0.7%), enter rectifying tower No. 1 by the toothed gear pump successive with 120 kilograms of/hour flows.270 ℃ of control tower still temperature, 110 ℃ of tower top temperatures of control, vacuum tightness be at 0.094MPa, reflux ratio 5: 1, and light constituent aniline, nitrogen benzide, three kinds of materials of azophenlyene are from the cat head extraction, and flow is about 26.2 kilograms/hour, enters rectifying tower No. 3.150 ℃ of No. 3 rectifying Tata still temperature, 90 ℃ of tower top temperatures, vacuum tightness 0.094MPa, reflux ratio 1: 1, cat head distills out aniline for 24 kilograms/hour with flow, what the tower still was remaining is nitrogen benzide, azophenlyene, and 1 rectifying tower tower bottoms enters rectifying tower No. 2, keeps 280 ℃ of tower still temperature, tower top temperature is controlled at 170 ℃, vacuum tightness is 0.097MPa, reflux ratio 1: 1, and it is finished product 4-aminodiphenylamine that the cat head of No. 2 rectifying tower obtains.No. 2 the rectifying tower bottoms enters batch still, the still temperature from 285-320 (℃), vacuum tightness 0.094MPa, the top temperature remain on 235-250 (℃), boil off remaining 4-aminodiphenylamine, apply mechanically back No. 2 rectifying tower and distill again.Whole piece refining 4-amino pentanoic technological process is continuous, 4-aminodiphenylamine yield height, good product quality.It is 99.1% that above-mentioned technology obtains finished product 4-ADP amine content, 72 ℃ of the fusing points of finished product, and 72.4 ℃ at zero pour, the industrial-scale production yield of this technological process is 92.1%.
Embodiment 2
In being furnished with 500 milliliters of three-necked flasks of condenser and agitator, add entry 230 grams, be not sequentially added into Tetramethylammonium hydroxide 91 grams (50%, 0.50 mole, all the other are water), sodium hydroxide 20 gram (0.5 mole), tetramethyl-volatile salt 52 grams (0.25 mole), control mixing temperature 72-77 (℃), stir, promptly make compound alkaline catalysts, concentration 29.9 (weight %).
Embodiment 3
Get nickel powder 46 grams, aluminium powder 51 grams, copper powder 3 grams, fusion in electric induction furnace is rolled into Powderedly after discharging, the cooling, handle, sieve, the order number remains on the 40-300 order, in capacity is 500 milliliters there-necked flask, thermometer and agitator are housed, and the 375 gram concentration of packing into are 20% the NaOH aqueous solution, slowly add to make powder, temperature of reaction remains on 60 ℃, reaction times is 4 hours, and the after washing catalyzer promptly gets composite powder powder catalyzer to neutral.
Claims (12)
1. one kind is the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, it is characterized in that selecting for use respectively and condensation, the corresponding two kinds of composite catalysts of hydrogenation, carry out condensation successively, hydrogenation, Separation and Recovery and apply mechanically compound alkaline catalysts and Separation and Recovery and apply mechanically regeneration after composite powder powder catalyzer, separate and recovery set hydrogenation solvent and aniline, the technological operation flow process that refining five operations are formed, the preparation method carries out continuously, wherein the composite catalyst of condensation reaction is compound alkaline catalysts, it is by tetraalkylammonium hydroxide, alkali metal hydroxide or its oxide compound, and the aqueous solution of tetraalkylammonium salt composition, the composite catalyst of hydrogenation is a composite powder powder catalyzer, its composition is a nickel, aluminium and " other metal or nonmetal " A, wherein A is Fe, Cu, Co, Mn, Cr, Mo, B, a kind of among the P.
2, according to claim 1 a kind of be the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, the mol ratio that it is characterized in that tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt in the described compound alkaline catalysts is (2-9): (0.5-3): (0.5-3), tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt three concentration expressed in percentage by weight summation are 15%-50%, if adopt alkalimetal oxide, then its consumption in catalyzer can convert by corresponding oxyhydroxide and get.
3, according to claim 1 and 2 a kind of be the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, the preparation method who it is characterized in that the compound alkaline catalysts that adopted is, with tetraalkylammonium hydroxide, alkali metal hydroxide, tetraalkylammonium salt, add in the entry, controlled temperature, stir, promptly get this compound alkaline catalysts.
4, according to claim 1 a kind of be the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, it is characterized in that in the described composite powder powder catalyzer, the weight percentage of nickel is 25%-99.9%, the weight percentage of aluminium and " other metal or nonmetal " A is 0.1%-75%, and the order number is 40 orders-300 orders.
5, according to claim 1 or 4 described be the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, the preparation method who it is characterized in that powder catalyst is: get nickel powder, aluminium powder and " other metal or nonmetal " A, fusion under the condition of high temperature, pulverize powdered after the discharging, handle obtaining with hydroxide aqueous solution.
6, according to claim 1 is the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, the condition that it is characterized in that condensation reaction is, oil of mirbane and aniline mol ratio are 1: 1-1: 15, temperature of reaction is 20 ℃-150 ℃, reaction pressure is absolute pressure 0.005MPa-0.1MPa, reaction times is 3.5 hours-6 hours, and the mol ratio of hydroxide ion and oil of mirbane is 1 in the compound alkaline catalysts: 4-4: 1.
7, according to claim 1 is the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, the gas-liquid volume ratio that it is characterized in that hydrogenation is 10: 1-1500: 1, the solid-liquid weight ratio is 0.5: 100-6: 100, the weight ratio of solvent and condensated liquid is 1: 10-5: 10, gas promptly refers to hydrogen, liquid comprises solvent and condensated liquid, solid promptly is meant composite powder powder catalyzer, the temperature of hydrogenation is 50 ℃-100 ℃, the pressure of the reactor of hydro-reduction is 0.2MPa-3.0MPa, and the reaction times of hydrogenation is 2 hours-7 hours.
8, according to claim 1 or 7 described be the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, it is characterized in that the separation of the hydride behind the hydrogenation, with water is extraction agent, the volume ratio of it and hydride is 0.5: 1-5: 1, with the polyethers organism for helping extraction agent, the volume ratio of its consumption and extraction agent water is 0.01: 1-0.05: 1, extracted time 2-5 hour.
9, according to claim 8 is the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, and the volume ratio that it is characterized in that extraction agent water and hydride is 0.8: 1-1.2: 1.
10, according to claim 8 is the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, it is characterized in that the described extraction agent that helps is polyglycol ether, polypropylene glycol ether, fatty alcohol-polyoxyethylene ether, polyethylene oxide dimethyl.
11, according to claim 1 is the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, it is characterized in that Separation and Recovery and apply mechanically compound alkaline catalysts employing one imitating or the multiple-effect concentrating unit, be used for the secondary steam that spissated heating agent is water, water vapour or last effect, its temperature is 60 ℃-150 ℃, spissated pressure is absolute pressure 0.005MPa-0.1MPa, and the spissated time is 2 seconds-60 seconds.
12, according to claim 1 is the method for feedstock production 4-aminodiphenylamine with oil of mirbane and aniline, it is characterized in that refining three tower continuous rectifications and the batch fractionating of adopting, it is 1 years old, 2, the vacuum tightness of No. 3 rectifying tower is respectively 0.09MPa-0.098MPa, 0.09MPa-0.098MPa, 0.09MPa-0.098MPa, tower still temperature is respectively 260 ℃-290 ℃, 260 ℃-300 ℃ and 120 ℃-170 ℃, reflux ratio is respectively 2: 1-10: 1,1: 0.5-1: 4 and 1: 0.5-1: 2, the tower still vacuum tightness of batch fractionating is 0.09MPa-0.098MPa, and tower still temperature is 280 ℃-330 ℃.
Priority Applications (20)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03148199 CN1202073C (en) | 2003-07-04 | 2003-07-04 | method for preparing 4-aminodiphenylamine |
| KR1020040051541A KR100612922B1 (en) | 2003-07-04 | 2004-07-02 | A process for producing 4-aminodiphenylamine |
| PCT/CN2004/000733 WO2005003078A1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| MXPA05013788A MXPA05013788A (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine. |
| JP2006500463A JP4500302B2 (en) | 2003-07-04 | 2004-07-02 | Method for producing 4-aminodiphenylamine |
| CA2515238A CA2515238C (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| EP04738331A EP1591438B1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| US10/883,042 US7084302B2 (en) | 2003-07-04 | 2004-07-02 | Process for preparing 4-aminodiphenylamine |
| BRPI0412101-5A BRPI0412101A (en) | 2003-07-04 | 2004-07-02 | process for the preparation of 4-aminodiphenylamine |
| EA200501647A EA009395B1 (en) | 2003-07-04 | 2004-07-02 | A process for preparing 4-aminodiphenylamine |
| DE602004010234T DE602004010234T2 (en) | 2003-07-04 | 2004-07-02 | PROCESS FOR THE PREPARATION OF 4-AMINODIPHENYLAMINE |
| ES04738331T ES2298762T3 (en) | 2003-07-04 | 2004-07-02 | PROCESS TO PREPARE 4-AMINODYPHENYLAMINE. |
| 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 |
| US11/759,897 US8293673B2 (en) | 2003-07-04 | 2007-06-07 | Process for preparing 4-aminodiphenylamine |
| US11/759,901 US20070227675A1 (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 |
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| CN100336796C (en) * | 2004-07-15 | 2007-09-12 | 王农跃 | Process for preparing 4-amino diphenylamine |
| CN102796011A (en) * | 2012-08-25 | 2012-11-28 | 山西翔宇化工有限公司 | Preparation method for p-aminodiphenylamine |
| CN104177263A (en) * | 2013-05-22 | 2014-12-03 | 中国石油化工股份有限公司 | Separation method of composition containing 4-aminodiphenylamine |
| CN106179332B (en) * | 2015-05-07 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of catalyst preparing 4-ADPA and preparation method |
| CN108623475A (en) * | 2017-03-20 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of method that quaternary ammonium alkali collection puts recycling in order |
| CN108997140B (en) * | 2017-06-06 | 2020-12-22 | 中国石油化工股份有限公司 | Method for separating, desalting and recycling recovered quaternary ammonium hydroxide |
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