CN105566125A - Method for compounding rubber antioxidant 6PPD and IPPD through nickel catalyst - Google Patents
Method for compounding rubber antioxidant 6PPD and IPPD through nickel catalyst Download PDFInfo
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- CN105566125A CN105566125A CN201410551894.3A CN201410551894A CN105566125A CN 105566125 A CN105566125 A CN 105566125A CN 201410551894 A CN201410551894 A CN 201410551894A CN 105566125 A CN105566125 A CN 105566125A
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Abstract
The invention belongs to the technical field of fine chemical engineering and relates to a method for compounding rubber antioxidants 6PPD and IPPD through a nickel catalyst. The 5%-60% of coprecipitation nickel catalyst is put into a static bed reaction device, and the catalyst is prereduced through the nitrogen and hydrogen drying method; after the prereduction program is finished, the temperature of a reaction system is reduced to the reaction temperature, and the coprecipitation nickel catalyst is adopted to compound the antioxidants 6PPD and IPPD. The nickel catalyst is adopted to the static bed device to compound the antioxidants 6PPD and IPPD, the adverse effects of a copper catalyst can be avoided, and compared with a noble metal catalyst, the cost of production raw materials can be greatly reduced.
Description
Technical field
The invention belongs to technical field of fine, relate to a kind of method adopting nickel catalyst synthetic rubber anti-aging agent.
Background technology
Rubber antioxidant 6PPD and IPPD is high-efficiency multi-function low-toxicity product, is mainly used in rubber industry, is kind important in current rubber antioxidant, and they are in natural and synthetic rubber, to ozone with subdue and agingly have good protective benefits.Adopt Virahol to carry out prereduction in current production technique, producing upper Virahol reduction at least needs one week, and carries out initial production production and can produce underproof product reducing end.Therefore the research of synthesis anti-aging agent 6PPD and IPPD catalyzer prereduction method is also got more and more.
Describe in patent CN102146042A with 4-ADPA and methyl iso-butyl ketone (MIBK) as raw material, 4-ADPA and methyl iso-butyl ketone (MIBK) mixing are carried out condensation reaction, it is characterized in that described condensation reaction pressure be 0 ~ 1MPa, temperature carries out under being the condition of 100 ~ 200 DEG C, after being shifted out by the water that condensation reaction generates, get condensated liquid; Again condensated liquid, hydrogenation catalyst and methyl iso-butyl ketone (MIBK) are dropped in reactor, pressure be 1 ~ 6MPa, temperature carries out hydrogenation reaction under being the condition of 80 ~ 180 DEG C, obtains hydrogenation liquid; After hydrogenation liquid being distilled, obtain p-phenylenediamine rubber aging inhibitor 4020; Described hydrogenation catalyst is nickel or palladium or platinum catalyst, and the input quality of hydrogenation catalyst accounts for 2 ~ 15% of methyl iso-butyl ketone (MIBK) total mass.
CN102260176A discloses a kind of anti-aging agent 6PPD continuous production technology, what this technique adopted is gas-liquid-solid three-phase fixed-bed hydrogenator, temperature of reaction 165 ~ 230 DEG C, pressure is 5.5 ~ 6.0MPa, ketoamine ratio is 2 ~ 4:1, hydrogen-oil ratio is 2000 ~ 5000:1, uses hydrogenation nickel catalyst in technique, can be used for the production of the annual output more than 7500 tons of anti-aging agent 6PPD.
US336684A and US4043942 has studied Ni/ diatomite catalyzer in great detail, and find that 4-aminodiphenylamine and reactive ketone yield reach 75%, and add some acid if 4-toluene sulfonic acide and some organosulfur compound are as after PhSMe, the yield increase of anti-aging agent is very large.
JP55100344Pt/C adopts the Pt/C catalyzer of 4% in the reductive amination process of 4-ADPA, ketone and hydrogen, and the selectivity of reaction improves greatly, and reaction yield also reaches 98%.
JP57156446 has prepared different types of activated carbon supported Pt, and preferable temperature is study its impact on reductive amination process under 190 DEG C of conditions, and wherein 6PPD yield is up to 98.3%, MIBC is 1.2%.
DE3728141 describes 4-ADPA in hydrogenation still, and acetone synthesis under normal pressure at 80 DEG C obtains 4010NA, makes catalyzer, in reaction system, add Mg with R or Pd/C
+ 2or Be
2+, hydrogenation speed improves greatly, and reaction yield reaches 96.2%.
Wu ties the catalyzer of the people such as China to 4-aminodiphenylamine and acetone through one-step method synthesis antioxidant 4010NA and has carried out laboratory study.Development copper system special-purpose catalyst, 4-aminodiphenylamine transformation efficiency is more than or equal to 98%, 4010NA selectivity and is more than or equal to 95%, and side reaction significantly reduces.
At present, domestic rubber antioxidant 6PPD and IPPD main manufacturer: Nanjing Chemical Industry Company of China Petrochemical Industry, Sheng Ao also all adopt this production technique, the catalyzer of synthesis anti-aging agent 6PPD and IPPD adopts Cu-series catalyst.Though Cu-series catalyst low price and not easily poisoning, be also convenient to continuous seepage operation, but quality product is slightly poor, yield is low.In addition, the Cu-series catalyst having minute quantity is in process of production pulverized and brings product into, has an impact to tire quality.
Summary of the invention
In the synthesis of anti-aging agent 6PPD and IPPD at home, mainly there is the remaining problem subsequent tyre quality of production being produced to harm of the Cu-series catalyst used in production technique at present, and the effective means solving this this problem reaches replenishment of process condition to realize exactly by development of new catalyzer.The present invention adopts co-precipitation nickel catalyst for fixed bed device synthesis anti-aging agent 6PPD and IPPD, can avoid the disadvantageous effect that Cu-series catalyst brings, greatly save raw materials for production cost compared with use noble metal catalyst.
Main technical schemes of the present invention: it is characterized in that 5% ~ 60% co-precipitation nickel catalyst to load in fixed-bed reactor, catalyzer adopts the prereduction of nitrogen hydrogen dry method, prereduction EP (end of program), reactive system temperature drops to temperature of reaction, adopts co-precipitation nickel catalyst synthesis anti-aging agent 6PPD and IPPD.
Usually, described prereduction pressure 0.5MPa, nitrogen, hydrogen flowing quantity are 0.5L/min, are full of and replace air in whole fixed bed reaction system, after reactive system displacement, heat up and carry out the prereduction of catalyzer.
Described synthesis reaction temperature is 90 ~ 160 DEG C, and pressure is 0.5 ~ 3.0MPa, and ketoamine ratio is 2 ~ 5.5: 1, and hydrogen-oil ratio is 1000 ~ 5000: 1.
Described nickel catalyst is co-precipitation nickel catalyst, comprises nickel, aluminium, magnesium, carbon etc.
Described reaction raw materials is 4-ADPA and the organism similar to it, hexone, acetone and the organism similar to it thereof.
The present invention adopts co-precipitation nickel catalyst for fixed bed device synthesis anti-aging agent 6PPD and IPPD, can avoid the disadvantageous effect that Cu-series catalyst brings, greatly save raw materials for production cost compared with use noble metal catalyst.
Embodiment
Below in conjunction with embodiment, the inventive method is described in detail.
embodiment 1
15% co-precipitation nickel catalyst is loaded in fixed-bed reactor, nitrogen is with 0.5MPa pressure, 0.5L/min flow is full of and replaces air in whole fixed bed reaction system, after reactive system displacement, heat up, nitrogen, hydrogen flowing quantity is 0.5L/min, pre-reduction temperature heats up by the temperature program set and carries out the prereduction of catalyzer, prereduction EP (end of program), reactive system temperature drops to temperature of reaction, temperature of reaction is 120 DEG C, pressure is 1.5MPa, ketoamine ratio is 5: 1, hydrogen-oil ratio is 2000: 1 synthetic tests carrying out IPPD, through stratographic analysis, reaction conversion ratio 50%, selectivity 70%.
embodiment 2
18% co-precipitation nickel catalyst is loaded fixed-bed reactor, nitrogen is full of juxtaposition with 0.5MPa pressure and changes whole fixed bed reaction system, after reactive system displacement, heat up, nitrogen, hydrogen flowing quantity are 0.5L/min, pre-reduction temperature heats up by the temperature program set and carries out the prereduction of catalyzer, prereduction EP (end of program), reactive system temperature drops to temperature of reaction, and temperature of reaction is 120 DEG C, pressure is 1.5MPa, ketoamine ratio is 5: 1, and hydrogen-oil ratio is 2000: 1 synthetic tests carrying out IPPD, through stratographic analysis, reaction conversion ratio 62%, selectivity 75%.
embodiment 3
20% co-precipitated catalyst is loaded fixed-bed reactor, nitrogen is full of juxtaposition with 0.5MPa pressure and changes whole fixed bed reaction system, after reactive system displacement, heat up, nitrogen, hydrogen flowing quantity are 0.5L/min, pre-reduction temperature heats up by the temperature program set and carries out the prereduction of catalyzer, prereduction EP (end of program), reactive system temperature drops to temperature of reaction, and temperature of reaction is 120 DEG C, pressure is 1.5MPa, ketoamine ratio is 5: 1, and hydrogen-oil ratio is 2000: 1 synthetic tests carrying out 6PPD, through stratographic analysis, reaction conversion ratio 75%, selectivity 74%.
embodiment 4
27% co-precipitation nickel catalyst is loaded fixed-bed reactor, nitrogen is full of juxtaposition with 0.5MPa pressure and changes whole fixed bed reaction system, after reactive system displacement, heat up, nitrogen, hydrogen flowing quantity are 0.5L/min, pre-reduction temperature heats up by the temperature program set and carries out the prereduction of catalyzer, prereduction EP (end of program), reactive system temperature drops to temperature of reaction, and temperature of reaction is 120 DEG C, pressure is 1.5MPa, ketoamine ratio is 5: 1, and hydrogen-oil ratio is 2000: 1 synthetic tests carrying out 6PPD, through stratographic analysis, reaction conversion ratio 80%, selectivity 79%.
Claims (5)
1. one kind adopts the method for nickel catalyst synthetic rubber anti-aging agent 6PPD and IPPD, 5% ~ 60% co-precipitation nickel catalyst is it is characterized in that to load in fixed-bed reactor, catalyzer adopts the prereduction of nitrogen hydrogen dry method, prereduction EP (end of program), reactive system temperature drops to temperature of reaction, adopts co-precipitation nickel catalyst synthesis anti-aging agent 6PPD and IPPD.
2. synthetic method as claimed in claim 1, it is characterized in that prereduction pressure 0.5MPa, nitrogen, hydrogen flowing quantity are 0.5L/min, are full of and replace air in whole fixed bed reaction system, after reactive system displacement, heat up and carry out the prereduction of catalyzer.
3. synthetic method as claimed in claim 1, it is characterized in that synthesis reaction temperature is 90 ~ 160 DEG C, pressure is 0.5 ~ 3.0MPa, and ketoamine ratio is 2 ~ 5.5: 1, and hydrogen-oil ratio is 1000 ~ 5000: 1.
4. synthetic method as claimed in claim 1, is characterized in that nickel catalyst is co-precipitation nickel catalyst, comprises nickel, aluminium, magnesium, carbon.
5. synthetic method as claimed in claim 1, is characterized in that reaction raw materials is 4-ADPA and the organism similar to it, hexone, acetone and the organism similar to it thereof.
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| CN201410551894.3A CN105566125A (en) | 2014-10-17 | 2014-10-17 | Method for compounding rubber antioxidant 6PPD and IPPD through nickel catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017546A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of method using noble metal catalyst synthetic rubber antioxidant 6PPD |
| CN111718265A (en) * | 2019-03-22 | 2020-09-29 | 中石化南京化工研究院有限公司 | Method for preparing high-purity anti-aging agent IPPD by catalytic hydrogenation of modified supported nickel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146042A (en) * | 2011-01-31 | 2011-08-10 | 江苏扬农化工集团有限公司 | Method for preparing p-phenylenediamine rubber aging inhibitor |
| CN102731323A (en) * | 2012-07-17 | 2012-10-17 | 山东尚舜化工有限公司 | Production process and equipment of anti-aging agent N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine |
-
2014
- 2014-10-17 CN CN201410551894.3A patent/CN105566125A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146042A (en) * | 2011-01-31 | 2011-08-10 | 江苏扬农化工集团有限公司 | Method for preparing p-phenylenediamine rubber aging inhibitor |
| CN102731323A (en) * | 2012-07-17 | 2012-10-17 | 山东尚舜化工有限公司 | Production process and equipment of anti-aging agent N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine |
Non-Patent Citations (2)
| Title |
|---|
| 朱书魁等: "橡胶防老剂4020/4010NA 及中间体合成技术", 《沈阳化工》 * |
| 须辑等: "《橡胶助剂制备新工艺》", 31 August 2014 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017546A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of method using noble metal catalyst synthetic rubber antioxidant 6PPD |
| CN111718265A (en) * | 2019-03-22 | 2020-09-29 | 中石化南京化工研究院有限公司 | Method for preparing high-purity anti-aging agent IPPD by catalytic hydrogenation of modified supported nickel |
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