CN1101379C - Process for continuously syntehsizing diphenylamine from phenylamine - Google Patents
Process for continuously syntehsizing diphenylamine from phenylamine Download PDFInfo
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- CN1101379C CN1101379C CN99113274A CN99113274A CN1101379C CN 1101379 C CN1101379 C CN 1101379C CN 99113274 A CN99113274 A CN 99113274A CN 99113274 A CN99113274 A CN 99113274A CN 1101379 C CN1101379 C CN 1101379C
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- reaction
- zeolite
- aniline
- catalyzer
- temperature
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 37
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010457 zeolite Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 229910001864 baryta Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- -1 solubility Chemical compound 0.000 description 1
- 238000003786 synthesis 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 continuously synthesizing diphenylamine from phenylamine. In the method, either a continuous process or an intermittent process can be adopted, wherein a catalyst in use is an H beta zeolite/gamma-Al2 O3 catalyst containing alkaline earth metals and chlorine. In the method, both the phenylamine conversion rate and the product selectivity are obviously improved, the byproduct yield is reduced, particularly, the catalyst life is prolonged to a large extent so that the production cost for the product is obviously reduced.
Description
The present invention relates to aniline is the method for raw material syntehsizing diphenylamine, particularly at H β zeolite/γ-AL
2O
3There is the method for syntehsizing diphenylamine down in catalyzer.
In industrial production, the conventional production methods of aniline syntehsizing diphenylamine is an intermittently process for catalytic synthesis of liquid phase, because this method uses aluminum chloride to be catalyzer, thereby make this technology have equipment corrosion and problem of environmental pollution (and needing after the reaction aluminum trichloride catalyst is separated) and raw material consumption height, product cost height from thick product.
In order to overcome the deficiency in the above-mentioned liquid phase synthesis process, US3118944, the US4454348 patent has adopted the aniline vapour phase syntehsizing diphenylamine method of the solid catalyst that with the aluminum oxide is major ingredient, though this method has solved the equipment corrosion problem, but temperature of reaction needs 360～450 ℃, and high like this temperature of reaction very easily causes reaction mass pyrolysis and polymerization, and then life of catalyst is shortened, the industrial application frequent regeneration causes the products production cost to raise.
The US3944613 patent has adopted the method for the aniline liquid phase syntehsizing diphenylamine that with the amorphous silicon aluminium is catalyzer, is 345 ℃, pressure 2.0MPa, volume space velocity 0.46h in temperature of reaction
-1Under the condition, the aniline transformation efficiency has only about 15%, though the temperature of reaction of this method is low than vapour phase processes, activity of such catalysts is lower.
941072967 (application numbers), CN1144715 patent have adopted with H β zeolite/γ-AL
2O
3Aniline liquid phase continuous synthesizing diphenylamine method for catalyzer, in temperature of reaction is 320～350 ℃, transformation efficiency in this method and selectivity obviously are better than US3118944, US4454348, US3944613 patent, and there are not equipment corrosion and problem of environmental pollution, but the catalyst life in its method is undesirable, and its one way longest-lived was failed 2000h, produces pentanoic if use this method in the industrialization, still need repeatedly regenerated catalyst, influential to the products production cost like this.
The objective of the invention is in order to overcome the deficiency of above-mentioned aniline continuous synthesizing diphenylamine method, a kind of aniline liquid phase continuous synthesizing diphenylamine method is provided,, improve the aniline transformation efficiency, reduce by-product, reduce production cost of products to prolong running period.
The present invention has adopted a kind of new catalyzer in the process of aniline syntehsizing diphenylamine, this catalyzer is the H β zeolite/γ-AL that contains chlorine and alkaline-earth metal
2O
3Consisting of of this catalyzer: the H β zeolite of a 50～90w%; The chlorine of b 2～4w%; The alkaline-earth metal of c 0.4～3.0w%; All the other are γ-AL for d
2O
3
The best group of this catalyzer becomes: the H β zeolite of a 60～88w%; The chlorine of b 2.5～3.5w%; The alkaline-earth metal of c 0.8～2.6w%; All the other are γ-AL for d
2O
3
Alkaline-earth metal wherein is preferably magnesium or barium.The SiO of H β zeolite
2/ AL
2O
3Molecular ratio is 20～100, is preferably 28～67.
The present invention's Preparation of catalysts method is: with H β zeolite and aluminium hydroxide (γ-AL
2O
3Precursor), the alkaline earth metal compound of ammonium chloride, solubility, nitric acid, deionized water mix pinch, moulding; Drying, roasting get the present invention's catalyzer.
The reaction of this syntehsizing diphenylamine can be adopted the liquid phase successive processes, and temperature of reaction is 290～350 ℃, and pressure is 1.5～5.0MPa, and air speed is 0.2～0.8h
-1Preferably temperature of reaction is 300～340 ℃, and pressure is 2.0～4.0MPa, and air speed is 0.37～0.68h
-1
The reaction of this syntehsizing diphenylamine also can be adopted the liquid phase intermittent process in addition, and catalyst levels is 20～80% of a raw material aniline weight, is preferably 30～60%, and temperature of reaction is 300～350 ℃, and pressure is 1.5～5.0MPa, and the reaction times is 1.5～3.5h.Preferably temperature of reaction is 320～340 ℃, and pressure is 2.0～4.0MPa, and the reaction times is 2.0～2.5h.
With the aniline continuous synthesizing diphenylamine, consequently aniline transformation efficiency and product selectivity all are significantly improved by the inventive method, and by-product descends to some extent, and especially the catalyst life increase rate is bigger, and the products production cost is significantly reduced.
Embodiment 1
Get 70g H β zeolite (SiO
2/ AL
2O
3Molecular ratio is 42) mix with the 20g aluminium hydrate powder, add ammonium chloride 3.8g, nitrate of baryta 2.5g and an amount of deionized water, mix on the banded extruder pinch after, extrusion, moulding make the catalyzer bar of diameter 1.5mm, at 50 ℃ of following dry 8.0h, 110 ℃ are descended dry 8.0h then.460 ℃ of following roasting 15h in muffle furnace more promptly obtain the present invention's catalyzer D-2, and wherein chloride is 2.9w%, and baric 1.5w% contains γ-AL
2O
314.5w%, all the other are H β zeolite.
Embodiment 2
Get 70g H β zeolite (SiO
2/ AL
2O
3Molecular ratio is 67) mix with the 20g aluminium hydrate powder, add ammonium chloride 3.8g, nitrate of baryta 2.5g and an amount of deionized water, mix on the banded extruder pinch after, extrusion, moulding make the catalyzer bar of diameter 1.5mm, at 60 ℃ of following dry 4.0h, 110 ℃ are descended dry 4.0h then.550 ℃ of following roasting 8.0h in muffle furnace more promptly obtain the present invention's catalyzer D-3, and wherein chloride is 2.9w%, and baric 1.5w% contains γ-AL
2O
314.5w%, all the other are H β zeolite.
Embodiment 3
Get 70g H β zeolite (SiO
2/ AL
2O
3Molecular ratio is 67) mix with the 20g aluminium hydrate powder, add ammonium chloride 3.8g, nitrate of baryta 4.1g and an amount of deionized water, all the other promptly obtain the present invention's catalyzer D-4 with embodiment 1, and wherein chloride is 2.9w%, and baric 2.5w% contains γ-AL
2O
314.4w%, all the other are H β zeolite.
Embodiment 4
Get 70g H β zeolite (SiO
2/ AL
2O
3Molecular ratio is 67) mix with the 20g aluminium hydrate powder, add ammonium chloride 3.5g, magnesium nitrate 8.0g and an amount of deionized water, all the other promptly obtain the present invention's catalyzer D-5 with embodiment 1, and wherein chloride is 2.9w%, contains magnesium 1.5w%, contains γ-AL
2O
314.6w%, all the other are H β zeolite.
Embodiment 5～9
Catalyst breakage among the embodiment 1～4 is become 40～60 orders, get a certain amount of catalyzer internal diameter 12mm that packs into, in the stainless steel reactor of long 650mm, reaction is charging down, and reaction mass flows out from reactor head, enters in the normal pressure separator after cooling, vapor phase ammonia is discharged from the separator top, the bottom liquid phases timing sampling is formed with gas chromatographic analysis, concrete reaction conditions and the results are shown in table 1.
Table 1
| Embodiment | The catalyzer numbering | The catalyzer Intake Quantity, g | Reaction conditions | Liquid product is formed, w% | The by-product rate, w% | ||||
| Temperature ℃ | Pressure MPa | Air speed h -1 | Aniline | Pentanoic | By-product | ||||
| ?5 | ?D-3 | ?30 | ?320 | ?2.0 | ?0.68 | ?75.43 | ?24.43 | ?0.14 | ?0.57 |
| ?6 | ?D-3 | ?30 | ?340 | ?4.0 | ?0.68 | ?68.27 | ?31.52 | ?0.21 | ?0.66 |
| ?7 | ?D-4 | ?30 | ?320 | ?2.5 | ?0.68 | ?76.75 | ?23.12 | ?0.13 | ?0.56 |
| ?8 | ?D-4 | ?30 | ?300 | ?2.0 | ?0.37 | ?69.68 | ?30.12 | ?0.20 | ?0.66 |
| ?9 | ?D-5 | ?30 | ?320 | ?2.0 | ?0.68 | ?81.54 | ?18.32 | ?0.14 | ?0.76 |
Annotate: by-product rate w%=(by-product/pentanoic) * 100%
Embodiment 10～14
Catalyst breakage among the embodiment 1～4 is become 40～60 orders, get its a certain amount of catalyzer and aniline thereof respectively, be encased in the 100ml autoclave., boost, temperature reaction air displacement in the reactor three times with nitrogen, reacted cooled and filtered, liquid product is used for gc analysis, concrete reaction conditions and the results are shown in table 2.
Table 2
| Embodiment | The catalyzer numbering | The aniline add-on, g | The catalyzer Intake Quantity, g | Reaction conditions | Liquid product is formed, w% | The by-product rate, w% | ||||
| Temperature ℃ | Pressure MPa | Time h | Aniline | Pentanoic | By-product | |||||
| ?10 | ?D-2 | ?50 | ?25 | ?320 | ?2.0 | ?2.5 | ?46.00 | ?53.41 | ?0.59 | ?1.11 |
| ?11 | ?D-3 | ?50 | ?25 | ?320 | ?2.0 | ?2.5 | ?44.24 | ?55.10 | ?0.66 | ?1.20 |
| ?12 | ?D-3 | ?50 | ?25 | ?340 | ?4.0 | ?2.0 | ?38.14 | ?61.11 | ?0.75 | ?1.22 |
| ?13 | ?D-4 | ?50 | ?15 | ?320 | ?3.0 | ?2.0 | ?74.76 | ?25.09 | ?0.15 | ?0.59 |
| ?14 | ?D-5 | ?50 | ?25 | ?320 | ?2.5 | ?2.5 | ?49.62 | ?49.64 | ?0.74 | ?1.50 |
Embodiment 15
With 110g, granularity is 8～40 purpose D-3 catalyzer internal diameter 25mm that pack into, in the stainless steel reactor of long 1500mm, the D-3 catalyzer is carried out the life-span service test.Reaction pressure is 2.0MPa, and the weight space velocity of reaction is 0.37h
-1, reacting and be charging down, reaction mass flows out from reactor head, enters in the normal pressure separator after cooling, and vapor phase ammonia is discharged from the separator top, and the bottom liquid phases timing sampling is formed with gas chromatographic analysis, concrete reaction conditions and the results are shown in table 3.
Table 3
| Temperature, ℃ | Accumulate runtime, h | Liquid product is formed, w% | The by-product rate, w% | ||
| Aniline | Pentanoic | By-product | |||
| ?310 | ?10 | ?66.62 | ?33.17 | ?0.21 | ?0.63 |
| ?310 | ?550 | ?70.79 | ?29.04 | ?0.17 | ?0.58 |
| ?315 | ?600 | ?67.96 | ?31.84 | ?0.20 | ?0.63 |
| ?315 | ?1300 | ?70.46 | ?29.35 | ?0.19 | ?0.64 |
| ?320 | ?1350 | ?67.00 | ?32.79 | ?0.21 | ?0.64 |
| ?320 | ?2450 | ?71.77 | ?28.06 | ?0.17 | ?0.61 |
| ?325 | ?2500 | ?69.28 | ?30.51 | ?0.21 | ?0.68 |
| ?325 | ?2800 | ?72.16 | ?27.64 | ?0.20 | ?0.72 |
Claims (8)
1. the method for an aniline syntehsizing diphenylamine is characterized in that adopting a kind of H β zeolite/γ-Al that contains chlorine and alkaline-earth metal
2O
3Catalyzer, this catalyzer consists of:
The H β zeolite of a 50～90w%;
The chlorine of b 2～4w%;
The alkaline-earth metal of c 0.4～3.0w%;
All the other are γ-Al for d
2O
3
The SiO of H β zeolite wherein
2/ Al
2O
3Molecular ratio is 20～100.
2. in accordance with the method for claim 1, it is characterized in that consisting of of catalyst system therefor:
The H β zeolite of a 60～88w%;
The chlorine of b 2.5～3.5w%;
The alkaline-earth metal of c 0.8～2.6w%;
All the other are γ-AL for d
2O
3
3. according to claim 1 or 2 described methods, it is characterized in that described alkaline-earth metal is magnesium or barium.
4. the SiO that it is characterized in that in accordance with the method for claim 1, described H β zeolite
2/ Al
2O
3Molecular ratio is 28～67.
5. in accordance with the method for claim 1, it is characterized in that the liquid phase successive processes is adopted in the reaction of aniline syntehsizing diphenylamine, temperature of reaction is 290～350 ℃, and pressure is 1.5～5.0MPa, and air speed is 0.2～0.8h
-1
6. in accordance with the method for claim 5, it is characterized in that described temperature of reaction is 300～340 ℃, pressure is 2.0～4.0MPa, and air speed is 0.37～0.68h
-1
7. in accordance with the method for claim 1, the liquid phase intermittent process is adopted in the reaction that it is characterized in that the aniline syntehsizing diphenylamine, and catalyst levels is 20～80% of a raw material aniline weight, and temperature of reaction is 300～350 ℃, pressure is 1.5～5.0MPa, and the reaction times is 1.5～3.5h.
8. in accordance with the method for claim 7, it is characterized in that described catalyst levels is 30～60% of a raw material aniline weight, temperature of reaction is 320～340 ℃, and pressure is 2.0～4.0MPa, and the reaction times is 2.0～2.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113274A CN1101379C (en) | 1999-09-29 | 1999-09-29 | Process for continuously syntehsizing diphenylamine from phenylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113274A CN1101379C (en) | 1999-09-29 | 1999-09-29 | Process for continuously syntehsizing diphenylamine from phenylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1289763A CN1289763A (en) | 2001-04-04 |
| CN1101379C true CN1101379C (en) | 2003-02-12 |
Family
ID=5276481
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113274A Expired - Lifetime CN1101379C (en) | 1999-09-29 | 1999-09-29 | Process for continuously syntehsizing diphenylamine from phenylamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1101379C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105272860A (en) * | 2014-06-30 | 2016-01-27 | 江苏飞亚化学工业有限责任公司 | Process for continuously producing diphenylamine with aniline |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114240A (en) * | 1994-06-29 | 1996-01-03 | 中国石油化工总公司抚顺石油化工研究院 | Catalyst for synthesizing diphenylamine from phenylamine and preparing process thereof |
| 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 |
-
1999
- 1999-09-29 CN CN99113274A patent/CN1101379C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114240A (en) * | 1994-06-29 | 1996-01-03 | 中国石油化工总公司抚顺石油化工研究院 | Catalyst for synthesizing diphenylamine from phenylamine and preparing process thereof |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 石油化工第23卷,第7期 1994-01-01 樊太山,梅来宝,周卓华苯胺缩合生产二苯胺催化剂的研究进展 * |
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| Publication number | Publication date |
|---|---|
| CN1289763A (en) | 2001-04-04 |
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