CN102319568A - Modified condensation reduction alkylation catalyst - Google Patents
Modified condensation reduction alkylation catalyst Download PDFInfo
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- CN102319568A CN102319568A CN201110195641A CN201110195641A CN102319568A CN 102319568 A CN102319568 A CN 102319568A CN 201110195641 A CN201110195641 A CN 201110195641A CN 201110195641 A CN201110195641 A CN 201110195641A CN 102319568 A CN102319568 A CN 102319568A
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Abstract
The invention belongs to the technical field of catalysts, and discloses a modified condensation reduction alkylation catalyst used in preparation of a rubber anti-aging agent 4020 by undergoing a hydrogenated reduction alkylation reaction on 4-aminodiphenylamine and methyl isobutyl ketone and preparation of a rubber anti-aging agent 4010NA by undergoing a hydrogenated reduction alkylation reaction on 4-aminodiphenylamine and acetone. The catalyst is a copper-series catalyst, and is mainly characterized in that: the catalyst contains a silicon element; and the molar ratio of copper to silicon is (0.5-10):1. Due to the adoption of the catalyst, a side reaction of ketone hydrogenation for generating an alcohol in the reacting process is suppressed remarkably, raw materials are saved, products 4010NA and 4020 are not required to be passivated by using 4-amino diphenylamine produced by reducing alkali sulfide at an earlier using stage, and unqualified products are avoided; and the catalyst has high intensity and long service life, and is not pulverized easily in the using process.
Description
Technical field
The invention belongs to catalyst technical field; Be that a kind of 4-of being used for aminodiphenylamine (RT training department) and hexone hydrogenating reduction alkylated reaction prepare rubber antioxidant 4020, and prepare the modified condensating reductive alkylation catalyst of rubber antioxidant 4010NA with 4-aminodiphenylamine (RT training department) and acetone hydrogenation reductive alkylation reaction.
Background technology
RT training department and aliphatic ketone condensating reductive alkylation product are the age resistor of p-phenylenediamine (PPD) class; In industry, use extremely extensive; Function admirable, commonly used is 4010NA and 4020. domestic production 4010NA and 4020 rubber antioxidants all adopt the technology of fixed-bed catalytic hydrogenation, and its chemical equation is:
Main reaction: 4010NA
4020
Main side reaction
Because ketone has not only been consumed a large amount of raw ketones and hydrogen by the existence of this side reaction of hydrogenation generation alcohol, causes the waste of raw material; Simultaneously because the mechanism of this reaction determines that side reaction makes the ketone molecule of catalyst surface not enough, causes forming ketoamine condensation intermediate product difficulty; So the principal product content behind the hydrogenation does not increase; And the impurity that also has other side reactions to produce simultaneously, separation brings difficulty to product, makes the catalyst use initial stage produce a lot of defective works.
U.S. Pat 3366684, US4043942 etc. are doing a lot of work aspect the side reaction of selectivity that improves main reaction and inhibition ketone hydrogenation; But the noble metal catalyst that is because of using still exists the catalyst costliness, and consumption of raw materials is high; The post processing inventory is big, and excessive ketone reclaims the shortcoming of trouble.
The said Cu-series catalyst of Chinese patent CN CN200610161327.2 exists the side reaction of easy efflorescence, ketone hydrogenation more serious at present, goes out problems such as qualified products cycle length.
Summary of the invention
The objective of the invention is to the problems referred to above; And a kind of 4-of the being used for aminodiphenylamine (RT training department) and the hexone hydrogenating reduction alkylated reaction that propose prepare rubber antioxidant 4020, and prepare the modified condensating reductive alkylation catalyst of rubber antioxidant 4010NA with 4-aminodiphenylamine (RT training department) and acetone hydrogenation reductive alkylation reaction.
Main technical schemes of the present invention: be used for 4-aminodiphenylamine (RT training department) and hexone hydrogenating reduction alkylated reaction and prepare rubber antioxidant 4020; And the condensating reductive alkylation catalyst for preparing rubber antioxidant 4010NA with 4-aminodiphenylamine (RT training department) and acetone hydrogenation reductive alkylation reaction; This catalyst is a Cu-series catalyst; Its main feature is to contain element silicon in the catalyst component, and the copper silicon mol ratio is 0.5-10:1.
Usually, catalyst Main Ingredients and Appearance of the present invention is a copper zinc silicon, and copper zinc mol ratio is 0.5-100:1; The copper silicon mol ratio is 0.5-10:1.
Catalyst of the present invention, be copper zinc mol ratio 0.64-22.4:1 preferred the composition; Copper silicon mol ratio 0.93-8.9:1; Most preferred composition is copper zinc mol ratio 0.8-1.2:1; Copper silicon mol ratio 2.0-3.0:1.
Copper, zinc element can add through the form of soluble metallic salt, and the used precipitating reagent of preparation catalyst can be selected sodium carbonate or sodium acid carbonate, and element silicon can add through the form of silica or siliceous salt or silicic acid.
Main feature of the present invention is: the side reaction that (1) ketone hydrogenation in course of reaction generates alcohol has obtained inhibition clearly, has practiced thrift raw material, and catalyst uses need not have substandard product with the RT training department passivation of sodium sulfide reducing production early stage; (2) catalyst strength is good, is difficult for efflorescence, long service life in the use.
Usually, catalyst of the present invention adopts the coprecipitation preparation, and concrete technological process is: with the copper nitrate water dissolve copper nitrate solution; With hot water preparing sodium carbonate solution or sodium bicarbonate aqueous solution, then copper nitrate solution is added (or in sodium bicarbonate solution) in the sodium carbonate liquor, also can be with sodium carbonate liquor (or sodium bicarbonate solution); Add copper nitrate solution, react to terminal pH=6.5-8.5 after, add silica; Filter material, the sodium ion in the flush away material, oven dry then; And, add suitable quantity of water and graphite afterwards 280-450 ℃ of following roasting, with the tablet of rotary tablet machine compacting Ф 5 * (4.5-5.5) mm.
Before using, catalyst needs to heat up stage by stage, till not consuming hydrogen and not going out reductive water through the i.e. certain density hydrogen of preparation in nitrogen of step of reducing.
Catalyst of the present invention: intensity is high, anti-efflorescence ability is good, the life-span is long; The side reaction of ketone hydrogenation has obtained good restraining, the residual ketone of back outlet just>=50% that feeds intake, and existing catalyst outlet residual ketone≤2% that just fed intake, and catalyst uses do not need passivation just can produce qualified products early stage; The preparation of employing coprecipitation, catalyst service condition: working pressure 3.0-6.0MPa, the feed rate speed 0.2-0.5h of RT training department
-1
The specific embodiment
Below in conjunction with embodiment the present invention is described in detail.
Slaine among following comparative example and the embodiment is nitrate trihydrate copper and zinc nitrate hexahydrate.
Comparative example 1:
The 500g copper nitrate, 660g zinc nitrate, 240g aluminum nitrate are dissolved in the 2L water; The 500g natrium carbonicum calcinatum is dissolved in the 5L water, then two kinds of solution is heated to 70 ℃ respectively, under agitation slowly splashes into sodium carbonate liquor in the mixed liquor of copper zinc-aluminium; Until pH=7.5. filtration washing then, 110 ℃ dry down, 350 ℃ of following roasting 4hr; Add 2% graphite, moulding on tablet press machine is of a size of Ф 5 * (4.5-5.5) mm.
Comparative example 2:
The 500g copper nitrate, the 660g zinc nitrate is dissolved in the 2L water jointly; Then two kinds of solution are heated to 70 ℃ respectively, sodium carbonate liquor is under agitation splashed in the copper zinc mixed liquor, until pH=7.2; And then add the 24g alumina powder, and the back filtration washing that stirs, 120 ℃ are dry down; 350 ℃ of roasting 2hr add 2% graphite moulding again, size Ф 5 * (4.5-5.5) mm.
Embodiment 1: 250g copper nitrate and 300g zinc nitrate are dissolved in the 1L water, are heated to 50 ℃, 400g sodium carbonate is dissolved in the 3L water; And be heated to 70 ℃, and then sodium carbonate is slowly dropped in the mixed solution of copper nitrate and zinc nitrate, stir fast simultaneously; Continue to stir 1 hour down until pH=7.5., add SiO 2 powder 30g then, stirred again 1 hour at 70 ℃; Follow filtration washing, solid material was dried 6 hours down at 120 ℃, 300 ℃ of following roastings 2 hours; Add 2% graphite and 4% water then and mix, be pressed into the tablet of Ф 5 * (4.5-5.5) mm, the catalyst copper zinc mol ratio 0.94 that makes like this with tablet press machine; Copper silicon mol ratio 2.1.
Embodiment 2: 500g copper nitrate and 25g zinc nitrate are dissolved in the 1L water, are heated to 50 ℃, the 550g sodium acid carbonate is dissolved in the 3L water; And be heated to 70 ℃, and then sodium bicarbonate solution is slowly dropped in the mixed solution of copper nitrate and zinc nitrate, stir fast simultaneously; Continue to stir 1 hour down until pH=7.5., add SiO 2 powder 150g then, stirred again 1 hour at 70 ℃; Follow filtration washing, solid material was dried 6 hours down at 120 ℃, 300 ℃ of following roastings 2 hours; Add 2% graphite and 4% water then and mix, be pressed into the tablet of Ф 5 * (4.5-5.5) mm, the catalyst copper zinc mol ratio 22.4 that makes like this with tablet press machine; Copper silicon mol ratio 0.83.
Embodiment 3: 200g copper nitrate and 350g zinc nitrate are dissolved in the 1L water, are heated to 50 ℃, 400g sodium carbonate is dissolved in the 3L water; And be heated to 70 ℃, and then sodium carbonate liquor is slowly dropped in the mixed solution of copper nitrate and zinc nitrate, stir fast simultaneously; Continue to stir 1 hour down until pH=7.5., add SiO 2 powder 5.6g then, stirred again 1 hour at 70 ℃; Follow filtration washing, solid material was dried 6 hours down at 120 ℃, 300 ℃ of following roastings 2 hours; The water that adds graphite and 2% then mixes, and is pressed into the tablet of Ф 5 * (4.5-5.5) mm, the catalyst copper zinc mol ratio 0.64 that makes like this with tablet press machine; Copper silicon mol ratio 8.9.
The performance of embodiment catalyst and comparative example catalyst compares:
Evaluation method: laboratory installation is simulated the large production equipment in the industry fully, and reactor is Ф 32 stainless steel tubes, and long 2m adorns original catalyst particle size 200ml. at every turn
Reaction condition: pressure 4.0MPa, 180 ℃ of temperature, hydrogen liquor ratio 1000, the mol ratio of acetone or hexone and RT training department is 5:1, liquid air speed 3.0h
-1(being equivalent to 6 times of actual production, mainly is the easy degree of grinding of under the condition of high load capacity, investigating catalyst).
At first, survey RT and 4010NA, 4020 content, survey ketone and pure relative amount from the cold catch pot sampling from high-temperature separator sampling.
Because liquid air speed and gas space velocity are all very big, thus very serious to washing away of catalyst, under the equal conditions, move after 13 days catalyst is drawn off its intensity of back survey.The efflorescence easily scarcely that intensity is high, long service life.Judge the degree of catalyst tolerates efflorescence according to the degree of carrying secretly of catalyst fines in the reactor discharge material.
Can find out from above contrast table:
1, comparative example acetone hydrogenation reaction in ten days of the initial stage of use is fierce, and first day remaining hexone of reactor outlet do not surpass 5% immediately less than 1% yet after 13 days; And embodiment just used first day, and the remaining hexone of reactor outlet is just greater than 50%, and especially embodiment just reached 60.2% in 1, the first day, in 13 days, just rose to 79.0% rapidly later on.
2, because the side reaction of hexone hydrogenation shows to such an extent that degree is different on different catalyst; Have influence on the carrying out of main reaction; The content embodiment 1 that finds out reactor outlet product 4020 significantly exceeded 6.7 percentage points in 1 first day than comparative example, exceeded 6.3 percentage points on the tenth day; Exceeded 5.1 percentage points in 2 first days than comparative example, exceeded 3.7 percentage points on the tenth day, three appearance are tended towards stability respectively after ten days.This mainly is that the impurity of generation is few because the catalyst selectivity of embodiment is good.Though embodiment 2 is a little bit poorer slightly than embodiment one with embodiment 3 4020 main content, compares with comparative example and still got well a lot.
Because experimental rig is less; Be difficult to overcome the wall stream effect of catalyst filling; So the catalyst conversion ratio fails to reach best effects, during industry practice is produced the conversion ratio of RT training department and 4020 main content be certain to better than experimental rig. but the comparing result of several examples is very convictive.
3, operation after 312 hours draws off catalyst, measures intensity.
Begin to have catalyst fines to occur in the material that comparative example 1: 45.6N/cm gave off after 96 hours
Begin to have catalyst fines to occur in the material that comparative example 2:58.3N/cm gave off after 72 hours
Embodiment 1:127.8N/cm did not observe after 312 hours yet has catalyst fines in the material
Embodiment 2:107.8N/cm observed after 264 hours has the trace catalyst powder to occur in the material
Embodiment 3:83.1.8N/cm observes after 144 hours and begins to have catalyst fines to occur in the material
Therefore can explain that the catalyst of the embodiment of the invention is difficult for efflorescence than the catalyst of comparative example, service life is longer.Especially embodiment 1, and effect is best.
Can find out from above contrast table:
1, comparative example acetone hydrogenation reaction in ten days of the initial stage of use is fierce, and the first day remaining acetone of reactor outlet did not surpass 5% immediately less than 1% yet after ten days; And embodiment has just come into operation, and the remaining acetone of reactor outlet just reaches more than 56%, in ten days, just rises rapidly later on.Especially embodiment one, just comes into operation, and the remaining acetone of reactor outlet just reaches 63.8%, in ten days, just rises to 80.5% rapidly later on.
2, because the side reaction of acetone hydrogenation shows to such an extent that degree is different on different catalyst; Have influence on the carrying out of main reaction; The content embodiment 1 that finds out reactor outlet product 4010NA significantly exceeded 11.3 percentage points in 1 first day than comparative example, exceeded 8.1 percentage points on the tenth day.Exceed 6.3 percentage points in 2 first days than comparative example, exceeded 5.2 percentage points on the tenth day.Three appearance are tended towards stability after ten days.Even embodiment 2 and embodiment 3, the principal product content of initial reaction stage, and react the principal product content after ten days, all be higher than two comparative examples significantly.This mainly is that the impurity of generation is few because the catalyst selectivity of embodiment is good.
3, operation after 312 hours draws off catalyst, measures intensity, and checks filter paper behind the filter material while hot.
Begin to have catalyst fines to occur in the material that comparative example 1: 50.1N/cm gave off after 72 hours
Begin to have catalyst fines to occur in the material that comparative example 2:41.3N/cm gave off after 48 hours
Embodiment 1:130.5N/cm did not observe after 312 hours yet has catalyst fines in the material
Embodiment 2:105.2N/cm observes after 240 hours and begins to have catalyst fines to occur in the material
Embodiment 3:87.1N/cm observed after 196 hours has the little amount of catalyst powder to occur in the material
Therefore can explain that the catalyst of the embodiment of the invention is difficult for efflorescence, service life is longer.Especially embodiment 1, and effect is best.
Claims (4)
1. improved condensating reductive alkylation catalyst; Be to be used for the 4-aminodiphenylamine and hexone hydrogenating reduction alkylated reaction prepares rubber antioxidant 4020; And the condensating reductive alkylation catalyst for preparing rubber antioxidant 4010NA with 4-aminodiphenylamine and acetone hydrogenation reductive alkylation reaction; This catalyst is a Cu-series catalyst, it is characterized in that containing element silicon in the catalyst component, and the copper silicon mol ratio is 0.5-10:1.
2. catalyst as claimed in claim 1 is characterized in that in the catalyst component, and copper zinc mol ratio is 0.5-100:1; The copper silicon mol ratio is 0.5-10:1.
3. catalyst as claimed in claim 1 is characterized in that in the catalyst component, copper zinc mol ratio 0.64-22.4:1; Copper silicon mol ratio 0.93-8.9:1.
4. catalyst as claimed in claim 1 is characterized in that in the catalyst component, copper zinc mol ratio 0.8-1.2:1; Copper silicon mole 2.0-3.0:1.
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| CN201110195641A CN102319568A (en) | 2011-07-13 | 2011-07-13 | Modified condensation reduction alkylation catalyst |
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| CN201110195641A CN102319568A (en) | 2011-07-13 | 2011-07-13 | Modified condensation reduction alkylation catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204778A (en) * | 2012-07-17 | 2013-07-17 | 山东尚舜化工有限公司 | Production process of anti-aging agent |
| CN106552626A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工集团公司 | SiO2For the application of the catalyst in synthetic rubber age resistor 6PPD of main carriers |
| CN107400261A (en) * | 2017-08-31 | 2017-11-28 | 李浩然 | A kind of preparation method of diphenylamine rubber age inhibitor for mountain bike |
| CN110152680A (en) * | 2019-06-25 | 2019-08-23 | 运城晋腾化学科技有限公司临猗分公司 | Copper-based catalysts, method of preparation and use for synthetic rubber anti-aging agent 6PPD |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103204778A (en) * | 2012-07-17 | 2013-07-17 | 山东尚舜化工有限公司 | Production process of anti-aging agent |
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| CN106552626A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工集团公司 | SiO2For the application of the catalyst in synthetic rubber age resistor 6PPD of main carriers |
| CN106552626B (en) * | 2015-09-29 | 2019-06-04 | 中国石油化工集团公司 | SiO2For application of the catalyst in synthetic rubber anti-aging agent 6PPD of main carriers |
| CN107400261A (en) * | 2017-08-31 | 2017-11-28 | 李浩然 | A kind of preparation method of diphenylamine rubber age inhibitor for mountain bike |
| CN110152680A (en) * | 2019-06-25 | 2019-08-23 | 运城晋腾化学科技有限公司临猗分公司 | Copper-based catalysts, method of preparation and use for synthetic rubber anti-aging agent 6PPD |
| CN110152680B (en) * | 2019-06-25 | 2021-02-12 | 运城晋腾化学科技有限公司临猗分公司 | Copper-based catalyst for synthesizing rubber antioxidant 6PPD, preparation and use method thereof |
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Application publication date: 20120118 |