CN114105782A - Antioxidant 6PPD synthesis method capable of reducing side reaction - Google Patents
Antioxidant 6PPD synthesis method capable of reducing side reaction Download PDFInfo
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- CN114105782A CN114105782A CN202111247326.0A CN202111247326A CN114105782A CN 114105782 A CN114105782 A CN 114105782A CN 202111247326 A CN202111247326 A CN 202111247326A CN 114105782 A CN114105782 A CN 114105782A
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- 238000007086 side reaction Methods 0.000 title claims description 6
- 238000001308 synthesis method Methods 0.000 title claims description 4
- 239000003963 antioxidant agent Substances 0.000 title description 15
- 230000003078 antioxidant effect Effects 0.000 title description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 6
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052802 copper Inorganic materials 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000002194 synthesizing effect Effects 0.000 abstract description 9
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000011049 filling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006268 reductive amination reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, and relates to a method for continuously synthesizing an anti-aging agent 6 PPD. The invention adopts noble metal catalyst to synthesize the age resister 6PPD on a fixed bed, the noble metal catalyst is loaded into a fixed bed reaction device, nitrogen is filled and replaces the whole high-pressure reaction kettle system at the pressure of 0.1-0.5 MPa, the temperature is raised after the reaction system is replaced, and the flow of introduced hydrogen is 0.1-1L/min. A synthesis test of synthesizing the age resister 6PPD by using a noble metal catalyst is carried out by using 4-aminodiphenylamine and similar organic matters thereof, methyl isobutyl ketone and acetone as raw materials. Compared with the prior noble metal kettle type hydrogenation process, the method has continuous operability and simple and convenient operation, avoids the catalyst loss caused by filtering by adopting a powder catalyst, and can reduce the production cost; compared with the existing copper catalyst, the catalyst has the advantages that the MIBC dehydrogenation device is not additionally arranged due to the improvement of the selectivity of the catalyst, the energy consumption is saved, and the catalyst has superiority.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and relates to a method for continuously synthesizing an antioxidant 6 PPD.
Background
The product has good antioxidant effect, and also has the effects of resisting ozone, flex cracking and inhibiting harmful metals such as copper, manganese and the like, can be widely used for preparing tires, adhesive tapes and other industrial rubber products, and is one of the main varieties of p-phenylenediamine antioxidants. Therefore, 6PPD, a main good variety commonly used in the rubber industry at home and abroad, is a key direction for the research and development of rubber antioxidants.
The rubber antioxidant 4020 is synthesized by adopting a one-step method of RT bis and MIBK in U.S. Pat. Nos. 3366684A and 4043942A, wherein the molar ratio of RT bis to MIBK is 1: 4, the temperature is 160-180 ℃, and the pressure is 4-5 MPa, and the reaction is carried out for 4 hours. The reduction of ketone is inhibited by changing the composition of the catalyst, thereby improving the selectivity of the reaction.
The patent CN102146042A starts from the practice of industrial production, and synthesizes a rubber antioxidant 4020 (6PPD) by adopting two-step reaction of condensation and hydrogenation; the hydrogenation catalyst is a nickel or palladium or platinum catalyst, and the input mass of the hydrogenation catalyst accounts for 2-15% of the total mass of the methyl isobutyl ketone.
Chinese patent application publication No. CN1170711A discloses an autoclave synthesis method of p-phenylenediamine rubber antioxidants, which also adopts a one-step method to carry out condensation hydrogenation reaction under the conditions of 2-10 MPa and 180-250 ℃ to synthesize the rubber antioxidants 4020, so as to reduce the dosage of MIBK (the molar ratio of RT bis to MIBK is 1: 1.05-1.1), although the yield of the product is good, the too small amount of MIBK causes the viscosity of the reaction solution to be extremely large, the fluidity is poor, and the recovery of the catalyst is very difficult. Furthermore, the amount of methyl isobutyl carbinol (MIBC) produced by the reaction is relatively large (alcohol/ketone molar ratio 1: 7) and separation is difficult.
Patent JP55100344 adopts 4% Pt/C catalyst in reductive amination of 4-aminodiphenylamine, ketone and hydrogen, and the selectivity of reacted 6PPD is greatly improved, and the yield also reaches 98%.
Patent JP57156446 prepared different kinds of activated carbon supported Pt, whose effect on the reductive amination reaction was studied preferably at a temperature of 190 ℃, with a 6PPD yield of up to 98.3% and 1.2% MIBC.
Patent CN102260176A describes a continuous production process of antioxidant 6PPD, which adopts a gas-liquid-solid three-phase fixed bed hydrogenation reactor and a nickel hydrogenation catalyst, the reaction temperature is 165-230 ℃, the pressure is 5.5-6.0 MPa, the ketoamine ratio is 2-4: 1, and the hydrogen-oil ratio is 2000-5000: 1, and the process can be used for the production of more than 7500 tons of antioxidant 6PPD per year.
Wujiehua et al have conducted laboratory studies on catalysts for synthesizing antioxidant 6PPD from RT base and methyl isobutyl ketone by one-step method. The developed copper special catalyst has RT conversion rate higher than or equal to 98%, 6PPD selectivity higher than or equal to 95% and obviously lowered side reaction. At present, the production process is adopted by domestic main rubber antioxidant 6PPD manufacturers, and a copper catalyst is adopted as a catalyst for synthesizing the antioxidant 6 PPD. Although the copper catalyst is cheap and not easy to be poisoned, and is convenient for continuous production operation, a very small amount of the copper catalyst is crushed in the production process and brought into products, thereby influencing the quality of downstream products.
In the synthesis of the foreign antioxidant 6PPD, the main production process at present is to generate a product by condensing and hydrogenating a noble metal catalyst in a batch reactor. The content of active components of the used catalyst needs to be as high as about 3 percent, the cost is high, the catalyst is powdery, the catalyst loss is easy to cause in the filtration, and the operation is complex. In the domestic synthesis of the age resister 6PPD, the main production process at present generates products by condensation hydrogenation of copper catalysts in a fixed bed reaction device. The catalyst used in the method can cause a small amount of residual copper in the product 6PPD, which is harmful to the production quality of subsequent tires, and the side reaction of ketone-alcohol conversion is severe, and an MIBC dehydrogenation device is required to be added, so that the equipment investment is increased, the production process is complex, the energy consumption is high, and the like.
Disclosure of Invention
In order to solve the technical problem, the invention adopts a method for continuously synthesizing the antioxidant 6PPD on a fixed bed by using a noble metal catalyst.
The technical scheme of the invention is as follows: a method for continuously synthesizing rubber antioxidant 6 PPD.
The main technical scheme of the method comprises the following contents:
a method for continuously synthesizing rubber antioxidant 6PPD by adopting a noble metal catalyst is characterized in that a reaction raw material is catalyzed by adopting the noble metal catalyst in a fixed bed reaction device to generate 6 PPD. And (2) loading the noble metal catalyst into a fixed bed reaction device, filling nitrogen into the fixed bed reaction device at the pressure of 0.1-0.5 MPa, replacing the whole high-pressure reaction kettle system, heating the reaction system after replacement, and introducing hydrogen at the flow rate of 0.1-1L/min. Taking 4-aminodiphenylamine and similar organic matters thereof, methyl isobutyl ketone, acetone and similar organic matters thereof as raw materials, and carrying out a synthesis test for synthesizing the antioxidant 6PPD by adopting a noble metal catalyst, wherein the reaction temperature is 60-150 ℃, the pressure is 0.5-1.5MPa, and the ketoamine ratio is 2.5-5.5: 1; the hydrogen-oil ratio is 1000-3000: 1.
Advantageous effects
Compared with the existing noble metal kettle type hydrogenation process, the method has the advantages that the NC201 prepared by Nanjing chemical research institute of China petrochemical industry is adopted to synthesize the antioxidant 6PPD on the fixed bed, the continuous operability is realized, the side reaction is effectively reduced, the operation is simple and convenient, the catalyst loss caused by filtering of a powder catalyst is avoided, and the production cost can be reduced; compared with the existing copper catalyst, the catalyst has the advantages that the MIBC dehydrogenation device is not additionally arranged due to the improvement of the selectivity of the catalyst, the energy consumption is saved, and the catalyst has superiority.
Detailed Description
Comparative example 1
Putting a 3% platinum catalyst into a high-pressure reaction kettle, filling nitrogen at 0.3MPa, replacing the whole high-pressure reaction kettle system, heating after the reaction system is replaced, introducing hydrogen with the flow rate of 0.4L/min, carrying out a 6PPD synthesis test under the conditions of the reaction temperature of 130 ℃, the reaction pressure of 3.0MPa, the mass ratio of the catalyst to RT of 1%, the ketoamine ratio of 1.5 and the stirring speed of 800-1000 r/min, and carrying out chromatographic analysis to obtain the product with the RT conversion rate of 99%, the 6PPD selectivity of 96%, the ketol ratio of 95/5 and the product purity of 98.89%.
Comparative example 2
The method comprises the steps of loading 30% of copper catalyst into a fixed bed reaction device, filling nitrogen at 0.4MPa, replacing the whole fixed bed reaction system, heating after the reaction system is replaced, introducing hydrogen at a flow rate of 0.3L/min, carrying out a 6PPD synthesis test under the conditions of 165 ℃ of temperature, 3.5MPa of pressure, 4:1 of ketoamine ratio of materials and 5000:1 of hydrogen-oil ratio, and carrying out chromatographic analysis to obtain a product with the RT conversion rate of 97%, the 6PPD selectivity of 95%, the ketol ratio of 25/75 and the product purity of 96.89%. Example 1
The method comprises the steps of loading 0.3% of platinum-carbon catalyst into a fixed bed reaction device, filling nitrogen at 0.2MPa, replacing the whole fixed bed reaction system, heating after the reaction system is replaced, introducing hydrogen at the flow rate of 0.2L/min, carrying out a 6PPD synthesis test under the conditions of the temperature of 115 ℃, the pressure of 1.1MPa, the ketoamine ratio of materials of 3.5: 1 and the hydrogen-oil ratio of 2000: 1, and carrying out chromatographic analysis to obtain the product with the RT conversion rate of 99.6%, the 6PPD selectivity of 99.42%, the ketol ratio of 99/1 and the product purity of 99.06%. Example 2
The method comprises the steps of loading a 0.3% platinum-carbon catalyst into a fixed bed reaction device, filling nitrogen at 0.4MPa, replacing the whole fixed bed reaction system, heating after the reaction system is replaced, introducing hydrogen at the flow rate of 0.5L/min, carrying out a 6PPD synthesis test under the conditions of the temperature of 145 ℃, the pressure of 1.8MPa, the ketoamine ratio of materials of 5.5: 1 and the hydrogen-oil ratio of 5000:1, and carrying out chromatographic analysis to obtain the product with the RT conversion rate of 100%, the 6PPD selectivity of 98.71%, the ketol ratio of 94/6 and the product purity of 98.56%.
Example 3
The method comprises the steps of loading 0.3% of platinum-carbon catalyst into a fixed bed reaction device, filling nitrogen at 0.9MPa, replacing the whole fixed bed reaction system, heating after the reaction system is replaced, introducing hydrogen with the flow rate of 0.8L/min, carrying out a 6PPD synthesis test under the conditions of the temperature of 145 ℃, the pressure of 0.3MPa, the ketoamine ratio of materials of 7.5: 1 and the hydrogen-oil ratio of 3000: 1, and carrying out chromatographic analysis to obtain the product with the RT conversion rate of 98%, the 6PPD selectivity of 96%, the ketol ratio of 98/2 and the product purity of 97.12%.
Example 4
The method comprises the steps of loading 0.27% of platinum-carbon catalyst into a fixed bed reaction device, filling nitrogen at 0.2MPa, replacing the whole fixed bed reaction system, heating after the reaction system is replaced, introducing hydrogen with the flow rate of 0.3L/min, carrying out a 6PPD synthesis test under the conditions of the temperature of 125 ℃, the pressure of 3.0MPa, the ketoamine ratio of materials of 5.5: 1 and the hydrogen-oil ratio of 5000:1, and carrying out chromatographic analysis to obtain the product with the RT conversion rate of 99%, the 6PPD selectivity of 97%, the ketol ratio of 92/8 and the product purity of 98.33%.
Example 5
The method comprises the steps of filling 0.3% of platinum-carbon catalyst into a fixed bed reaction device, filling nitrogen at 0.4MPa, replacing the whole fixed bed reaction system, heating after the reaction system is replaced, introducing hydrogen with the flow rate of 0.4L/min, carrying out a 6PPD synthesis test under the conditions of 95 ℃ of temperature, 3.0MPa of pressure, 5.5: 1 of ketoamine ratio of materials and 5000:1 of hydrogen-oil ratio, and carrying out chromatographic analysis to obtain the product with the RT conversion rate of 98%, the 6PPD selectivity of 98%, the ketol ratio of 86/14 and the product purity of 98.5%.
Example 6
The method comprises the steps of filling 0.25% of platinum-carbon catalyst into a fixed bed reaction device, filling nitrogen at 0.3MPa, replacing the whole fixed bed reaction system, heating after the reaction system is replaced, introducing hydrogen with the flow rate of 0.4L/min, carrying out a 6PPD synthesis test under the conditions of 120 ℃ of temperature, 2.0MPa of pressure, 4.5: 1 of ketoamine ratio of materials and 5000:1 of hydrogen-oil ratio, and carrying out chromatographic analysis to obtain the product with the RT conversion rate of 99%, the 6PPD selectivity of 97%, the ketol ratio of 95/5 and the product purity of 98.75%.
Example 7
The method comprises the steps of loading 0.25% of platinum-carbon catalyst into a fixed bed reaction device, filling nitrogen at 0.9MPa, replacing the whole fixed bed reaction system, heating after the reaction system is replaced, introducing hydrogen with the flow rate of 0.8L/min, carrying out a 6PPD synthesis test under the conditions of 120 ℃ of temperature, 2.0MPa of pressure, 4.5: 1 of ketoamine ratio of materials and 5000:1 of hydrogen-oil ratio, and carrying out chromatographic analysis to obtain the product with the RT conversion rate of 98%, the 6PPD selectivity of 98%, the ketol ratio of 95/5 and the product purity of 98.83%.
Claims (7)
1. A synthesis method of an age resister 6PPD for reducing side reactions, which adopts a noble metal catalyst to carry out ketoamine condensation hydrogenation reaction on reaction raw materials in a fixed bed reaction device to generate the age resister 6PPD, comprises the following steps: the noble metal catalyst is loaded into a fixed bed reaction device, the whole reaction system is replaced under the pressure of less than or equal to 0.3MPa of nitrogen, and after the reaction system is replaced, the raw materials of 4-aminodiphenylamine, hydrogen and methyl isobutyl ketone are synthesized into the age inhibitor 6PPD in a reactor at a certain temperature and under a certain pressure.
2. The method of claim 1, wherein: the certain temperature is 60-150 ℃.
3. The method of claim 2, wherein: the certain pressure is 0.5-1.5 Mpa.
4. The method of claim 1, wherein: the mass content of platinum in the noble metal catalyst is 0.1-5%.
5. The method of claim 1, wherein: the mass ratio of the methyl isobutyl ketone to the 4-aminodiphenylamine is more than or equal to 90: 10.
6. The method of any one of claims 1 to 5, wherein: and introducing the hydrogen into the reaction system, wherein the flow of the introduced hydrogen is 55-65L/min.
7. The method of any one of claims 1 to 5, wherein: the noble metal catalyst also contains Fe and S elements, wherein the content of Fe is less than or equal to 0.2 percent, and the content of S is 0.2-0.6 percent.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554286A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工集团公司 | A kind of method that noble metal catalyst continuously prepares p phenylenediamine type antioxidant |
| 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 |
| CN110818571A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | Method for synthesizing p-phenylenediamine anti-aging agent by adopting Pt/C catalyst |
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- 2021-10-26 CN CN202111247326.0A patent/CN114105782A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554286A (en) * | 2015-09-29 | 2017-04-05 | 中国石油化工集团公司 | A kind of method that noble metal catalyst continuously prepares p phenylenediamine type antioxidant |
| 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 |
| CN110818571A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | Method for synthesizing p-phenylenediamine anti-aging agent by adopting Pt/C catalyst |
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