CN100387570C - Method for preparing diphenylamine by aniline liquid phase condensation and denitrification coupling - Google Patents
Method for preparing diphenylamine by aniline liquid phase condensation and denitrification coupling Download PDFInfo
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- CN100387570C CN100387570C CNB2004100418644A CN200410041864A CN100387570C CN 100387570 C CN100387570 C CN 100387570C CN B2004100418644 A CNB2004100418644 A CN B2004100418644A CN 200410041864 A CN200410041864 A CN 200410041864A CN 100387570 C CN100387570 C CN 100387570C
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000010168 coupling process Methods 0.000 title claims abstract description 19
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 15
- 230000008878 coupling Effects 0.000 title claims abstract description 14
- 238000009833 condensation Methods 0.000 title claims description 29
- 230000005494 condensation Effects 0.000 title claims description 29
- 239000007791 liquid phase Substances 0.000 title claims description 19
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 title abstract description 11
- 238000006481 deamination reaction Methods 0.000 claims abstract description 43
- 230000009615 deamination Effects 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000006482 condensation reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims abstract description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010457 zeolite Substances 0.000 claims abstract description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 29
- 238000010992 reflux Methods 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 230000011514 reflex Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- 230000009466 transformation Effects 0.000 description 17
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000004044 response Effects 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- -1 hexamethylene aniline Chemical compound 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- RAOIAWFHTATHBD-UHFFFAOYSA-N NC1=CC=CC=C1.[I] Chemical compound NC1=CC=CC=C1.[I] RAOIAWFHTATHBD-UHFFFAOYSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FMMQDMHSGNXJSQ-UHFFFAOYSA-N n,n-diphenylhydroxylamine Chemical compound C=1C=CC=CC=1N(O)C1=CC=CC=C1 FMMQDMHSGNXJSQ-UHFFFAOYSA-N 0.000 description 1
- RPFGCUFAJAQNLJ-UHFFFAOYSA-N n-phenylcyclohexanimine Chemical compound C1CCCCC1=NC1=CC=CC=C1 RPFGCUFAJAQNLJ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DQLGIONSPPKALA-UHFFFAOYSA-N phenylazanium;phenoxide Chemical compound NC1=CC=CC=C1.OC1=CC=CC=C1 DQLGIONSPPKALA-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a method for producing diphenylamine by coupling a condensation reaction and deamination. The aim of the method is to improve the single pass conversion rate of phenylamine, reduce the energy consumption needed by the separation of unreacted phenylamine, improve the utilization rate of a catalyst and improve the productive capacity of devices, thereby, the production cost for the diphenylamine is reduced. The method has the characteristics of simple device, easy operation control, etc. In the method, the devices for coupling the condensation reaction and the deamination are connected in series by 2 to N fixed bed reactors, and each reactor is filled with a beta-zeolite molecular sieve catalyst; the top of each reactor is provided with a gas-liquid separator and a reflex condenser, and the gas-liquid separator is provided with a liquid level displaying and controlling system. The operation pressure of each reactor is controlled to be from 1.5 to 3.0MPa, the reaction temperature is controlled to be from 260 to 400DEG C, and the space velocity of the added phenylamine as a raw material is controlled to be from 0.1 to 2.0 grams/gram catalyst. H.
Description
Technical field
The present invention relates to the synthetic of organic compound, the method for saying so in more detail and adopting aniline liquid phase condensation and deamination coupling technique to produce pentanoic.
Background technology
Pentanoic has another name called the N-phenylaniline, and molecular formula is C
12H
11N.It is a kind of important meticulous Organic Chemicals, and is of many uses, is mainly used in industries such as rubber ingredients, explosive stablizer, medicine, dyestuff.As rubber ingredients, the diphenylamine anti-aging agent has heat resistanceheat resistant oxygen, the anti-effect of circumnutating preferably, and ageing of metal and ozone-induced cracking are also had some protection effect; As the explosive stablizer, pentanoic itself and its degraded product are agent of explosive satisfactory stability and propellant; Be mainly used in dyestuffs such as synthetic acidic yellow G, acid IV, the bright orchid of sulfuration at dye industry; Be mainly used in the preparation thiodiphenylamine in pharmaceutical industries, further synthetic wormer, agrochemical; In addition, pentanoic also as the additive of finishing metal, is used to prepare agricultural chemicals and other organic compound etc., and its derivative is (as the isopropoxy pentanoic, list or diheptyl pentanoic, hydroxy diphenylamine, oxyammonia pentanoic) be widely used in rubber and the plastics industry as antioxidant.
The pentanoic synthetic route of bibliographical information has nearly 20 kinds more than, promotes thermal response method, arylamine deaminizating method etc. as hexahydroaniline method, inferior hexahydroaniline method, cyclohexylidene aniline process, dicyclohexyl amine method, phenylhydroxylamine method, hexamethylene aniline process, aniline iodine.But most of industrial values are little, and industrialization at present or the method with industrial prospect mainly contain aniline condensation method, aniline phenol condensation method and aniline pimelinketone condensation method etc.Wherein the aniline condensation method is divided vapour phase condensation and liquid phase condensation method again, and vapour phase condensation is owing to will pass through earlier the preheating vaporization process with raw material before the reaction, and temperature of reaction is also higher, energy consumption height not only, and easily cause and the coking of material cause catalyst deactivation; The liquid phase condensation method does not need material gasification, and temperature of reaction is lower, has overcome vapour phase condensation method energy consumption height, the easy shortcoming of coking, and the catalyzer life cycle is long, has than remarkable advantages.
The reaction that aniline condensation prepares pentanoic is a reversible exothermic reaction:
320～350 ℃ of industrial control reaction pressure 2.0～2.5MPa, temperature of reaction, owing to be subjected to the restriction of chemical equilibrium, the aniline per pass conversion generally can only be below 25%, the aniline raw material that is equivalent to 3～4 times of pentanoic product volumes need recycle through rectifying separation, the burden of later separation operation is very heavy, and energy expenditure is very high.
Though improving temperature, prolonging the residence time is the effective way that improves transformation efficiency, concerning reversible exothermic reaction, temperature is too high can to influence the molecular balance transformation efficiency, and selectivity also can descend, and must raise for the pressure of keeping liquid phase condensation system simultaneously; Residence time lengthening, when transformation efficiency improved, the throughput of catalyzer will descend, because catalyzer price height, only be 1 year work-ing life, and use about three months and just need regenerate once, the decline of catalyst productivity certainly will increase the shared cost of catalyzer.Therefore seeking new approach and strengthen the aniline condensation reaction process, improve the aniline per pass conversion, is very necessary for improving plant capacity, reducing energy consumption and production costs.
According to chemical equilibrium theory, if one of product that aniline condensation reaction is generated ammonia is in time removed from reaction system, chemical equilibrium will be moved to the direction that generates pentanoic.The content of ammonia is few more in the reaction system, and the transformation efficiency of aniline was high more when then reaction arrived balance, and the amount of product pentanoic is many more.Simultaneously ammonia content also can exert an influence to speed of response in the reaction system, ammonia shift out the quickening that helps the aniline condensation speed of response.
For the condensation reaction of aniline liquid phase, raw material aniline and product pentanoic are in the liquid phase, the ammonia of by-product is overflowed from liquid phase and has just been realized the separation of ammonia, therefore as long as in the aniline condensation reaction unit, increase deamination equipment, just condensation of aniline liquid phase and deamination can be coupled, when condensation reaction takes place, follow deamination, reduce the ammonia content in the reaction system, thereby improve the transformation efficiency of aniline condensation reaction.Ideal aniline condensation one deamination coupling process should be the coupling (as shown in Figure 1) of continuous condensating reaction and deamination, and this need adopt horizontal top to have the reactor of gas-phase space.Such successive processes also can be with the coupling process equivalence (as shown in Figure 2) of a plural serial stage, as long as placed in-line progression is abundant, both effects are the same.
Summary of the invention
The objective of the invention is at aniline liquid phase condensation reaction, the method that provides a kind of condensation reaction and deamination to be coupled is produced pentanoic, to improve the aniline per pass conversion, reduce and separate the required energy consumption of unreacted aniline, improve catalyst utilization and plant capacity, thereby reduce the production cost of pentanoic.It is simple that this method has a device, characteristics such as easy operation control.
Purpose of the present invention can reach by following measure:
Condensation reaction of the present invention and deamination coupling device adopt 2～N platform, and (N is generally below 10, be preferably 3～4) the fixed-bed reactor series connection, dress beta-zeolite molecular sieve catalyst in every reactor, the top of reactor is provided with gas-liquid separator and reflux exchanger, and gas-liquid separator is equipped with liquid level to show and Controlling System.The working pressure of every reactor all is controlled at 1.5～3.0MPa, is preferably between 2.0～2.5MPa; Temperature of reaction is controlled at 260～400 ℃, is preferably between 300～350 ℃; The air speed that adds raw material aniline is controlled at 0.1～2.0 gram/gram catalyzer hour, is preferably between 0.2～0.8 gram/gram catalyzer hour.The aniline raw material with volume pump metering and be pressurized to reaction pressure, is preheating to temperature of reaction, delivers into first reactor bottom, from passing through the beds in the reactor down.When reaction mixture arrived the gas-liquid separator of reactor head, ammonia separated with liquid phase mixture, after aniline, pentanoic are reclaimed in the reflux exchanger condensation of process reactor head, left reactive system deammoniation gas recovery system and obtained the liquefied ammonia byproduct.Be the normal operation that keeps producing, the aniline in the gas-liquid separator, the liquid level of diphenylamine compound need to keep stable by the operation of Controlling System.Reaction mixture behind deamination enters second reactor, after deamination enters follow-up the 3rd～N platform reactor successively, carries out condensation reaction and deamination.The reaction mixture that comes out from last reactor enters follow-up deamination, take off component before the aniline, separate aniline, take off operations such as light component and pentanoic product purification, finally obtains the pentanoic product.
For placed in-line aniline condensation reactor assembly, can adopt isopyknic reactors in series, as adopt 3-4 platform fixed-bed reactor to connect, every reactor can load the catalyzer of same amount, its advantage is that in such system the flow direction of reaction mass can be changed according to the catalyzer service condition.When catalyzer reaches 2～3 months duration of service, the whole appearance of catalyst activity in the reactor descends, but the catalyst reactor activity after leaning on is better relatively, can be introduced into raw material last reactor this moment, flow forward successively, the pentanoic that contains unreacted aniline at last leaves from first reactor and enters separation system.Such blocked operation can prolong the catalyzer life cycle, reduces the number of times of catalyst regeneration.
When aniline raw material during successively through the fixed-bed reactor of 1～N platform equal volume, the concentration of aniline descends gradually by 1,2 to N order in the reactor, and speed of response slows down successively, generate pentanoic and also reduce successively, every reactor removes the then minimizing synchronously of amount of ammonia.In order to demonstrate fully deamination to improving the effect of speed of response, aniline transformation efficiency and pentanoic growing amount, condensation-deamination coupling reaction system can adopt the reactors in series of different volumes, the catalyzer that loads in placed in-line 1,2 to the N platform fixed-bed reactor can be according to 2
N-1Multiple increase successively.Such combination of reactors form has been strengthened the effect of deamination to condensation reaction, switches but reaction mass can not be carried out countercurrent flow, has influenced the handiness of production operation.
When in above-mentioned condensation-deamination coupling device, carrying out aniline condensation reaction production pentanoic, under same reaction pressure, temperature and air speed condition, the aniline per pass conversion brings up to 25～30% from 20～23%, the pentanoic product volume that generates increases by 10～30%, catalyst utilization and plant capacity improve too, reduce isolating amount of unreacted aniline and energy consumption 20～30%.
Advantage of the present invention is: the reactor assembly that has gas-liquid separator and reflux exchanger that adopts plural serial stage, produce pentanoic according to condensation of aniline liquid phase and deamination coupled method, its device is simple, convenient operation and control, aniline per pass conversion, catalyst utilization and plant capacity significantly improve, separating energy consumption descends greatly, and production cost is low, the economic benefit height.
Description of drawings
Fig. 1 is continuous condensating-deamination coupling process synoptic diagram.
Fig. 2 is the condensation-deamination coupling process synoptic diagram of plural serial stage.
Embodiment
In order to further specify the present invention, be illustrated below by example:
Example one:
To be numbered four fixed-bed reactor of 1,2,3,4 and connect successively, and load beta-zeolite molecular sieve catalyst 6 grams, 12 grams, 24 grams and 48 grams respectively, the catalyzer total filling amount is 90 grams.Controlling each reactor pressure is that 2.0MPa, temperature are 330 ℃, raw material aniline adds first reactor bottom with the speed of 36 Grams Per Hours (air speed be 0.4 gram/gram catalyzer hour) after pressurization, heating, successively through the beds of four reactors, and leave the composition of sampling analysis reaction mixture from the 4th reactor top.1,2, the top of No. 3 reactors is equipped with reflux exchanger and valve respectively, and valve opening just can be stablized deamination to certain aperture when carrying out the aniline condensation reaction.Deamination and not under two kinds of operation formats of deamination resulting aniline transformation efficiency be respectively 29.3% and 25.1%, visible because deamination is coupled with condensation reaction to carry out, make the aniline transformation efficiency improve 4.2%.
Example two:
Adopt the device same with example one, loaded catalyst, reaction pressure are also identical with example one with temperature.Raw material aniline joins in the reactive system with the speed of 54 Grams Per Hours (air speed be 0.6 gram/gram catalyzer hour), deamination and not under two kinds of operation formats of deamination resulting aniline transformation efficiency be respectively 23.8% and 18.4%, as seen because deamination and condensation reaction coupling are carried out, make the aniline transformation efficiency improve 5.4%.
The result of comparative example one and example two as can be seen, under the lower situation of aniline transformation efficiency, deamination is more favourable to the raising of transformation efficiency.
Example three:
With two fixed-bed reactor series connection that are filled with 5250 kilograms of beta-zeolite molecular sieve catalysts, the top of every reactor is provided with gas-liquid separator, reflux exchanger and tank level control system.Working pressure in the controlling reactor and temperature are respectively 2.0MPa and 320 ℃, raw material aniline adds the bottom of first reactor with 2950 kilograms/hour speed (air speed be 0.28 gram/gram catalyzer hour) after pressurized, heated, behind the beds through two reactors, leave reactive system from second reactor head.Metering by analysis, obtain deamination and not the aniline transformation efficiency under two kinds of operational circumstances of deamination be respectively 26.6% and 24.5%, deamination and condensation are coupled and make the aniline transformation efficiency improve 2.1%.
Example four:
With three fixed-bed reactor series connection that are filled with 5100 kilograms of beta-zeolite molecular sieve catalysts, the top of every reactor is provided with gas-liquid separator, reflux exchanger and tank level control system.Working pressure in the controlling reactor and temperature are respectively 2.0MPa and 320 ℃, raw material aniline adds the bottom of first reactor with 4300 kilograms/hour speed (air speed be 0.28 gram/gram catalyzer hour) after pressurized, heated, behind the beds through three reactors, leave reactive system from the 3rd reactor head.Metering by analysis, obtain deamination and not the aniline transformation efficiency under two kinds of operational circumstances of deamination be respectively 28.5% and 24.8%, deamination and condensation are coupled and make the aniline transformation efficiency improve 3.7%.
The result of comparative example three and example four as seen, placed in-line reactor platform number increases, removing of the ammonia that aniline condensation generates is more timely, is favourable to improving the aniline transformation efficiency.
Claims (6)
1. aniline liquid phase condensation and deamination are coupled and produce the method for pentanoic, wherein condensation reaction adopts 2～N platform fixed-bed reactor to connect with the deamination coupling device, be filled with beta-zeolite molecular sieve catalyst in every reactor, the top of reactor is provided with gas-liquid separator and reflux exchanger, gas-liquid separator is equipped with liquid level to show and Controlling System, the working pressure of every reactor all is controlled at 1.5～3.0MPa, temperature of reaction is controlled at 260～400 ℃, the air speed that adds raw material aniline is controlled at 0.1～2.0 gram/gram catalyzer hour, and wherein N is below 10.
2. the method that pentanoic is produced in aniline liquid phase according to claim 1 condensation and deamination coupling is characterized in that adopting 3～4 fixed-bed reactor to connect the catalyzer of every reactor charge same amount.
3. the method that pentanoic is produced in the coupling of aniline liquid phase according to claim 1 condensation and deamination is characterized in that placed in-linely 1,2, and the catalytic amount that loads in～N platform the fixed-bed reactor is according to 2
N-1Multiple increase successively, wherein N is below 10.
4. the method that pentanoic is produced in aniline liquid phase according to claim 1 condensation and deamination coupling, the working pressure that it is characterized in that reactor is between 2.0～2.5MPa.
5. the method that pentanoic is produced in aniline liquid phase according to claim 1 condensation and deamination coupling, the service temperature that it is characterized in that reactor is between 300～350 ℃.
6. the method that pentanoic is produced in the coupling of aniline liquid phase according to claim 1 condensation and deamination, the air speed that it is characterized in that reaction unit is between 0.2～0.8 gram/gram catalyzer hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100418644A CN100387570C (en) | 2004-09-03 | 2004-09-03 | Method for preparing diphenylamine by aniline liquid phase condensation and denitrification coupling |
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| CNB2004100418644A CN100387570C (en) | 2004-09-03 | 2004-09-03 | Method for preparing diphenylamine by aniline liquid phase condensation and denitrification coupling |
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| CN100387570C true CN100387570C (en) | 2008-05-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102816073A (en) * | 2012-08-27 | 2012-12-12 | 万隆化工有限公司 | Synthesis method of para-tertiary butyl aniline |
| CN103642047B (en) * | 2013-11-28 | 2016-06-29 | 南京林业大学 | A kind of preparation method of double; two (alkyl polyoxy alkane alkene ether) secondary amine |
| CN116063189A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Method for improving selectivity of synthesizing diphenylamine from phenylamine |
| CN116425637A (en) * | 2022-01-01 | 2023-07-14 | 中国石油化工股份有限公司 | Method and device for preparing diphenylamine and phenothiazine from aniline |
| CN114805086A (en) * | 2022-05-16 | 2022-07-29 | 杰超橡塑南通有限公司 | Process and system for producing diphenylamine by adopting aniline continuous condensation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3944613A (en) * | 1973-09-10 | 1976-03-16 | New Japan Chemical Company, Limited | Process for preparing diphenylamine from aniline |
| CN1144796A (en) * | 1995-09-05 | 1997-03-12 | 中国石油化工总公司抚顺石油化工研究所 | Method for synthetic diphenylamine with aniline |
| CN1289642A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Catalyst for continuously synthesizing diphenylamine from phenylamine and its preparing process |
-
2004
- 2004-09-03 CN CNB2004100418644A patent/CN100387570C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3944613A (en) * | 1973-09-10 | 1976-03-16 | New Japan Chemical Company, Limited | Process for preparing diphenylamine from aniline |
| CN1144796A (en) * | 1995-09-05 | 1997-03-12 | 中国石油化工总公司抚顺石油化工研究所 | Method for synthetic diphenylamine with aniline |
| CN1289642A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Catalyst for continuously synthesizing diphenylamine from phenylamine and its preparing process |
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