CN109701669B - Regeneration method of hydrogenation catalyst for preparing arylamine antioxidant - Google Patents
Regeneration method of hydrogenation catalyst for preparing arylamine antioxidant Download PDFInfo
- Publication number
- CN109701669B CN109701669B CN201910146267.4A CN201910146267A CN109701669B CN 109701669 B CN109701669 B CN 109701669B CN 201910146267 A CN201910146267 A CN 201910146267A CN 109701669 B CN109701669 B CN 109701669B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrogenation catalyst
- antioxidant
- solvent
- washing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalysts, and particularly discloses a regeneration method of a hydrogenation catalyst for preparing an arylamine antioxidant. The invention adopts the solvent with better solubility to macromolecular organic matters (polyaniline) blocking the catalyst pore channels as the hot washing agent, and realizes the functions of cleaning coking and dredging the pore channels; the cleaned catalyst is subjected to hydrothermal treatment to reconstruct a weak acid site (mainly phenolic hydroxyl) on the carbon surface so as to effectively recover the acid catalysis performance of the ketoamine condensation reaction. The method has the characteristics of simple and convenient operation, mild conditions, environmental protection, high efficiency and the like, does not damage the material structure of the carbon carrier and the load state of active metal nano particles while dredging the pore structure of the catalyst and reconstructing acid sites, highly conforms to the characteristic of ketoamine reductive amination reaction, and can effectively recover the activity of the catalyst.
Description
(I) technical field
The invention relates to the technical field of catalysts, in particular to a regeneration method of a hydrogenation catalyst for preparing an arylamine antioxidant.
(II) background of the invention
The aromatic amine rubber antioxidant is an important rubber antioxidant class, mainly comprises IPPD, 6PPD, 7PPD, 77PD and the like, and is widely applied to the rubber and tire industry. At present, the aromatic amine rubber antioxidant is produced by mainly using aromatic amine and aliphatic ketone as raw materials through a reductive amination reaction. The production technology for preparing the arylamine rubber antioxidant by the traditional reductive amination method generally adopts a copper catalyst as a hydrogenation catalyst. The catalyst is actually a low-temperature CO conversion catalyst such as B204, C207 and the like in the ammonia synthesis industry, and mainly comprises CuO-ZnO-Al2O3The initial development and the later development of the method are not customized for the preparation of the aromatic amine rubber antioxidant, and are more difficult to be combined withThe characteristics of the original alkylation reaction are matched, and the main problems are as follows: (1) the catalyst has poor selectivity and serious side reaction of ketone carbonyl hydrogenation; (2) the reaction conditions are harsh due to low catalytic activity; (3) loss of active ingredient results in severe "copper damage".
Due to the defects of the copper-based catalytic process, the quality of the low-quality arylamine antioxidant produced by the traditional copper-based catalyst is poor, and the use of the antioxidant produced by the copper-based catalytic process is limited in order to avoid the copper harm of tires by international tire enterprises with well-known brands; meanwhile, the anti-aging capability and the service life of the tire product using the low-quality antioxidant are greatly influenced, the competitiveness of the tire product is greatly weakened, and the life safety of drivers and passengers is threatened.
In order to overcome the defects of the traditional copper catalyst hydrogenation process, a process for preparing the arylamine antioxidant by the noble metal catalytic reduction amination reaction is researched and developed. Among them, Pt/C and Pd/C catalysts are widely used. Due to the excellent hydrogenation activity and reaction selectivity of platinum metals, compared with the production process of copper catalysts, the quality of the antioxidant product is greatly improved, and the hydrogenation side reaction of the ketocarbonyl is effectively inhibited. However, since the noble metal supported catalyst is expensive, the service life thereof is directly related to the production cost of the antioxidant. With the increase of the recycling times of the catalyst, the activity of the catalyst is continuously deteriorated, and the catalytic performance is gradually reduced. Therefore, how to effectively regenerate the catalyst with deteriorated activity to recover the catalytic activity and prolong the service life of the catalyst is the key for developing a novel process for producing the aromatic amine rubber antioxidant by catalyzing the aromatic amine rubber antioxidant by the noble metal.
Disclosure of the invention
The invention provides a regeneration method of a hydrogenation catalyst for preparing an arylamine antioxidant, which has simple process and long service life and is used for making up the defects of the prior art.
The invention is realized by the following technical scheme:
a regeneration method of hydrogenation catalyst for preparing arylamine antioxidant takes hydrogenation catalyst recovered in the preparation process of arylamine antioxidant as a processing object, and comprises the following steps:
(1) dispersing a hydrogenation catalyst into a solvent A to form a suspension, conveying the suspension into a regeneration kettle 1 which is replaced by nitrogen in advance, and heating, stirring and washing; feeding the mixed material liquid after washing into a precision filter for filtering, then backflushing the catalyst into the regeneration kettle 1 by using a solvent B, heating, stirring, washing and filtering again;
(2) backflushing the catalyst into a high-pressure regeneration kettle 2 which is replaced by nitrogen in advance by using deionized water, and heating for hydrothermal treatment; and after the hydrothermal treatment is finished, feeding the mixed material liquid into a precision filter for filtering to obtain the regenerated catalyst.
The invention adopts the solvent with better solubility to macromolecular organic matters (polyaniline) blocking the catalyst pore channels as the hot washing agent, and realizes the functions of cleaning coking and dredging the pore channels; the cleaned catalyst is subjected to hydrothermal treatment to reconstruct a weak acid site (mainly phenolic hydroxyl) on the carbon surface so as to effectively recover the acid catalysis performance of the ketoamine condensation reaction. The hydrothermal treatment condition is mild, the pore structure of the carrier and the loading state of the active metal nano particles are not damaged while the surface of the carbon carrier is functionalized, and the risks of damage to the physical structure of the carrier and aggravation of agglomeration and loss of active components caused by conventional oxidation treatment of nitric acid, hydrogen peroxide and the like can be effectively avoided.
The more preferable technical scheme of the invention is as follows:
the recovered hydrogenation catalyst is one of Pt/C, Pd/C, modified Pt/C and modified Pd/C, and the isoelectric point of the recovered hydrogenation catalyst is greater than 6.5.
In the step (1), the solvent A is one of N-methyl pyrrolidone, N-dimethylformamide and dipropylene glycol dimethyl ether, and the mass ratio of the hydrogenation catalyst to the solvent A is 1: 10-100; the temperature for stirring and washing is 60-200 ℃.
The solvent B is one of methanol, ethanol and isopropanol, and the mass ratio of the hydrogenation catalyst to the solvent B is 1: 10-100; the temperature for stirring and washing is 50-120 ℃.
In the step (2), the mass ratio of the hydrogenation catalyst to the deionized water is 1:10-100, and the temperature of the hydrothermal treatment is 180-260 ℃.
The isoelectric point of the regenerated catalyst is less than 6, and the regenerated catalyst is used for the synthetic reaction of antioxidant IPPD, 6PPD, 7PPD or 77 PD.
The invention combines TEM, SEM, XRD and N2A plurality of technical means such as low-temperature physical adsorption, TGA, GC-MS, ICP-OES and the like comprehensively compare and characterize fresh and deactivated catalysts, and carefully research the activity deterioration mechanism of the hydrogenation catalyst for preparing the aromatic amine antioxidant finds that the main reason of the catalyst activity reduction in the reaction process is as follows: the pore channel structure of the catalyst is blocked by organic impurities, the specific surface area and the pore volume of the catalyst are greatly reduced, and the active sites in the pore channels are sealed and lose effectiveness. Because the reaction condition of ketoamine reductive amination catalyzed by the noble metal catalyst is mild, the active metal nanoparticles of the catalyst do not have the phenomena of sintering, agglomeration, growth and the like in the using process.
By N2The analysis results of low-temperature physical adsorption, TGA, GC-MS and the like show that macromolecular organic impurities cause the blockage of the pore channel structure of the catalyst. The inventor discovers through deep research on a reaction mechanism that a ketone amine reductive amination reaction related to a preparation process of the arylamine antioxidant is formed by connecting two steps of reactions in series, firstly, ketone and amine generate a dehydration condensation reaction to generate imine, namely Schiff base, the reaction is a nucleophilic addition reaction catalyzed by a weak acid condition, and then, an imine structure generates a reduction reaction. Although the two reaction processes are carried out in series, the two reaction processes have an equilibrium matching relationship: the dynamic balance of adsorption and desorption of reactants and products on a hydrogenation active center can be maintained only if the Schiff base generation speed is matched with a reasonable hydrogenation speed, otherwise, the hydrogenation products are easy to generate deep reaction on the active site of the catalyst, namely side reactions such as coking polymerization and the like. Once macromolecular impurities are generated by side reactions, the macromolecular impurities have certain polymerization degree due to large molecular weight, and are poor in solubility, so that the macromolecular impurities are difficult to elute and remove by common organic solvents such as alcohol, ketone, ester and the like. Therefore, the method is an effective way for avoiding the pore channel structure of the catalyst from being blocked by organic impurities by reasonably optimizing the reaction process according to the characteristics of the ketoamine reductive amination reaction and inhibiting side reactions such as coking polymerization of the hydrogenation product on the active site of the catalyst.
For Pt/C and Pd/C catalysts for preparing the arylamine antioxidant, acidic oxygen-containing groups on the surface of the activated carbon are important acid catalytic sites generated by Schiff bases, and the acidic oxygen-containing groups can promote the protonation degree of the raw material ketone carbonyl carbon and accelerate the ketone-amine condensation reaction rate. However, the reaction system contains aromatic amine which has certain alkalinity, part of acid sites can be consumed along with the reaction, and the decomposition of part of acid sites can be accelerated by high temperature and high pressure in the reaction process. The conclusion is also verified by adopting the technical methods of Boehm's joint alkali titration, mass titration and the like to carry out comparative analysis on the fresh and used catalysts, the number of oxygen-containing groups on the surface of the used catalyst is greatly reduced, and the isoelectric point is increased. The reduction of the acid sites on the surface of the catalyst inevitably causes the reduction of the generation rate of the Schiff base, thereby indirectly aggravating side reactions such as coking polymerization and the like on the hydrogenation active sites, and finally causing the activity of the catalyst to be deteriorated and even inactivated.
The method has the characteristics of simple and convenient operation, mild conditions, environmental protection, high efficiency and the like, does not damage the material structure of the carbon carrier and the load state of active metal nano particles while dredging the pore structure of the catalyst and reconstructing acid sites, highly conforms to the characteristic of ketoamine reductive amination reaction, can effectively recover the activity of the catalyst, greatly increases the application times of the hydrogenation catalyst for preparing the arylamine antioxidant, and obviously reduces the consumption cost of the catalyst.
(IV) description of the drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a TEM photograph of Pt/C-1U in example 5 of the present invention;
FIG. 2 is a TEM photograph of Pt/C-1U/5RA in example 5 of the present invention;
FIG. 3 is a TEM photograph of Pt/C-1U/5RB in example 5 of the present invention.
(V) detailed description of the preferred embodiments
The present invention will be further described with reference to the following examples.
Example 1: the method for preparing the antioxidant IPPD by regenerating the Pt/C catalyst comprises the following steps:
(1) 1kg of catalyst to be treatedThe agent (Pt/C-1U, isoelectric point 7.2) was dispersed in 50kg of N-methylpyrrolidone to form a suspension, which was transferred into a pre-applied N-methylpyrrolidone2Heating the replaced 100L regeneration kettle 1 to 120 ℃, stirring and washing; and (3) feeding the mixed material liquid after washing to a precision filter for filtering, back flushing the catalyst to the regeneration kettle 1 by using 50kg of methanol, raising the temperature to 60 ℃, stirring, washing and filtering.
(2) The catalyst was backflushed with 50kg of deionized water to a preliminary N2Heating the replaced 100L high-pressure regeneration kettle 2 to 230 ℃ for hydrothermal treatment; after the completion of the hydrothermal treatment, the mixed solution was filtered through a microfilter to obtain a regenerated catalyst, designated as Pt/C-1R, which was measured to have an isoelectric point of 5.5.
And (3) evaluating the performance of the regenerated catalyst: the mol ratio of the acetone to the 4-aminodiphenylamine is 5:1, the mass ratio of the dry-based catalyst to the 4-aminodiphenylamine is 1:100, the reaction temperature is 90 ℃, the hydrogen pressure is 1.5MPa, and the catalyst is continuously used for 5 times without being supplemented. Quantitative analysis is carried out on 5 batches of hydrogenation liquid by adopting a gas chromatography method, the conversion rate of 4-aminodiphenylamine and the IPPD purity of the product are calculated, and the specific analysis conditions are as follows: the vaporization temperature is 300 ℃, the temperature of an FID detector is 300 ℃, the initial column temperature is 80 ℃, the initial column temperature is maintained for 2min, the heating rate is 15 ℃/min, the final column temperature is 300 ℃, the final column temperature is maintained for 5min, and the capillary chromatographic column model HP-5 (30 m multiplied by 0.32mm multiplied by 0.25 mu m) is adopted. The results are as follows.
The experimental results in the table show that the regenerated catalyst is continuously used for 5 times without being supplemented, 4-aminodiphenylamine is completely converted, the chromatographic analysis purity of the product IPPD is higher than 99%, the reaction time is basically unchanged along with the increase of the application frequency of the catalyst, the catalyst stability is excellent, and the catalytic performance is obviously recovered compared with that before regeneration.
Example 2: comparative experiment of regeneration method
The Pt/C-1U catalyst was washed and regenerated by the method of step (1) of example 1, and the isoelectric point of the treated catalyst was determined to be 7, which was designated as Pt/C-2R.
The performance of the regenerated Pt/C-2R was evaluated: the evaluation test and analysis method were the same as in example 1. The results are as follows.
As can be seen from the experimental results in the above table, when the treated Pt/C-2R is used, the reaction lasts for 6.2 hours, about 10% of 4-aminodiphenylamine is not converted, and the chromatographic purity of the product IPPD is only 88.7%, although the purity is slightly improved compared with that before the treatment, the catalyst activity recovery effect is not obvious. It is explained that the desired regeneration effect cannot be achieved only by the washing treatment alone.
Example 3:
the Pt/C-1U and Pt/C-1R before and after regeneration in example 1 are respectively used as ketoamine condensation reaction catalysts to evaluate the generation performance of the acid-catalyzed Schiff base: the mol ratio of the acetone to the 4-aminodiphenylamine is 5:1, the mass ratio of the dry-based catalyst to the 4-aminodiphenylamine is 1:100, the reaction temperature is 90 ℃, and nitrogen in the kettle is replaced.
Sampling is carried out once every 30min by a sampling port, and the generation amount of Schiff base in the reaction solution is analyzed by adopting a gas chromatography, wherein the specific analysis conditions are as follows: the vaporization temperature is 300 ℃, the temperature of an FID detector is 300 ℃, the initial column temperature is 80 ℃, the initial column temperature is maintained for 2min, the heating rate is 15 ℃/min, the final column temperature is 300 ℃, the final column temperature is maintained for 5min, and the capillary chromatographic column model HP-5 (30 m multiplied by 0.32mm multiplied by 0.25 mu m) is adopted. The Pt/C-1U before regeneration was evaluated, and the results are shown below.
The experimental results in the table show that the generation rate and the equilibrium generation amount of the regenerated catalyst in the presence of catalytic Schiff base are obviously improved compared with those before regeneration, and the regeneration effect of the hydrothermal treatment on the acidic sites on the surface of the catalyst is verified.
Example 4: the method for preparing antioxidant 6PPD by regenerating Pt/C catalyst comprises the following steps:
(1) 2kg of the catalyst to be treated (designated as Pt/C-3U, isoelectric point 7.4) was dispersed in 200kg of dipropylene glycol dimethyl ether to form a suspension, which was transferred into a reactor previously treated with N2Heating the replaced 500L regeneration kettle 1 to 140 ℃, stirring and washing; and (3) feeding the mixed material liquid after washing to a precision filter for filtering, then backflushing the catalyst into the regeneration kettle 1 by using 40kg of ethanol, raising the temperature to 70 ℃, stirring, washing and filtering.
(2) The catalyst was backflushed with 80kg of deionized water to the point where N had previously been used2Heating the replaced 200L high-pressure regeneration kettle 2 to 240 ℃ for hydrothermal treatment; after the completion of the hydrothermal treatment, the mixed solution was filtered through a microfilter to obtain a regenerated catalyst, designated as Pt/C-3R, which was measured to have an isoelectric point of 5.7.
And (3) evaluating the performance of the regenerated catalyst: the molar ratio of the methyl isobutyl ketone to the 4-aminodiphenylamine is 4:1, the mass ratio of the dry-based catalyst to the 4-aminodiphenylamine is 1:100, the reaction temperature is 110 ℃, the hydrogen pressure is 3MPa, and the catalyst is continuously applied for 5 times without being supplemented. Quantitative analysis is carried out on 5 batches of hydrogenation liquid by adopting a gas chromatography, the conversion rate of 4-aminodiphenylamine and the purity of 6PPD of the product are calculated, and the specific analysis conditions are as follows: vaporization temperature 300 deg.C, FID detector temperature 300 deg.C, initial column temperature 100 deg.C, heating rate 18 deg.C/min, final column temperature 300 deg.C, final column temperature maintaining time 10min, and capillary chromatographic column model HP-5 (30 m × 0.32mm × 0.25 μm). The results are as follows.
The experimental results in the table show that the regenerated catalyst is continuously used for 5 times without being supplemented, 4-aminodiphenylamine is basically completely converted, the purity of the product 6PPD chromatographic analysis is higher than 99%, the reaction time is basically unchanged along with the increase of the application times of the catalyst, the catalyst is good in stability, and the catalytic performance is obviously recovered compared with that before regeneration.
Example 5:
the catalyst Pt/C-1U100g to be treated in example 1 was weighed out exactly in three portions. The first part of the catalyst is regenerated and reacted according to the regeneration method and the IPPD synthesis reaction conditions in the embodiment 1, the catalyst is discharged after 5 times of accumulative regeneration (the catalyst is used for 30 times in total), and is marked as Pt/C-1U/5RA for analysis; the second part of catalyst is regenerated according to the traditional oxidation treatment method: the catalyst is treated by nitric acid or hydrogen peroxide with the concentration of 5-30% at the temperature of room temperature-80 ℃, the treated catalyst is reacted according to the IPPD synthesis reaction conditions in the example 1, and the catalyst is discharged after being cumulatively regenerated for 5 times (the total time of the catalyst is 20 times), which is marked as Pt/C-1U/5RB for analysis.
Analysis was performed by transmission electron microscopy on Pt/C-1U, Pt/C-1U/5RA and Pt/C-1U/5 RB. As can be seen from the attached figure, in Pt/C-1U and Pt/C-1U/5RA, Pt nano-crystalline grains are uniformly dispersed, and in Pt/C-1U/5RB, Pt nano-crystalline grains are locally and obviously agglomerated.
And respectively placing the accurately weighed third part of Pt/C-1U and the regenerated and reacted Pt/C-1U/5RA and Pt/C-1U/5RB in three quartz crucibles, slowly burning and removing carbon in a muffle furnace, completely dissolving the residual metal residues with equivalent aqua regia respectively, diluting and fixing the volume to the same volume, carrying out quantitative analysis on the Pt concentration in the solution by adopting ICP-OES, and calculating the Pt content in the original catalyst, wherein the result is as follows.
As can be seen from the data in the table above, the Pt content of the catalyst Pt/C-1U/5RB regenerated and used by the conventional oxidation treatment method is obviously reduced compared with the original catalyst Pt/C-1U, and the conventional oxidation treatment method can be judged to aggravate the loss of the active metal.
Claims (5)
1. A regeneration method of hydrogenation catalyst for preparing arylamine antioxidant takes hydrogenation catalyst recovered in the preparation process of arylamine antioxidant as a treatment object, and is characterized by comprising the following steps:
(1) dispersing a hydrogenation catalyst into a solvent A to form a suspension, conveying the suspension into a regeneration kettle 1 which is replaced by nitrogen in advance, and heating, stirring and washing; feeding the mixed material liquid after washing into a precision filter for filtering, then backflushing the catalyst into the regeneration kettle 1 by using a solvent B, heating, stirring, washing and filtering again;
the solvent A is one of N-methyl pyrrolidone, N-dimethylformamide and dipropylene glycol dimethyl ether;
the solvent B is one of methanol, ethanol and isopropanol;
(2) backflushing the catalyst into a high-pressure regeneration kettle 2 which is replaced by nitrogen in advance by using deionized water, and heating for hydrothermal treatment; after the hydrothermal treatment is finished, feeding the mixed material liquid into a precision filter for filtering to obtain a regenerated catalyst;
the recovered hydrogenation catalyst is one of Pt/C, Pd/C, modified Pt/C and modified Pd/C, and the isoelectric point of the recovered hydrogenation catalyst is greater than 6.5.
2. The method for regenerating a hydrogenation catalyst for the preparation of an aromatic amine antioxidant, as claimed in claim 1, wherein: in the step (1), the mass ratio of the hydrogenation catalyst to the solvent A is 1: 10-100; the temperature for stirring and washing is 60-200 ℃.
3. The method for regenerating a hydrogenation catalyst for the preparation of an aromatic amine antioxidant, as claimed in claim 1, wherein: in the step (1), the mass ratio of the hydrogenation catalyst to the solvent B is 1: 10-100; the temperature for stirring and washing is 50-120 ℃.
4. The method for regenerating a hydrogenation catalyst for the preparation of an aromatic amine antioxidant, as claimed in claim 1, wherein: in the step (2), the mass ratio of the hydrogenation catalyst to the deionized water is 1:10-100, and the temperature of the hydrothermal treatment is 180-260 ℃.
5. The method for regenerating a hydrogenation catalyst for the preparation of an aromatic amine antioxidant, as claimed in claim 1, wherein: in the step (2), the regenerated catalyst has an isoelectric point less than 6 and is used for the synthesis reaction of antioxidant IPPD, 6PPD, 7PPD or 77 PD.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910146267.4A CN109701669B (en) | 2019-02-27 | 2019-02-27 | Regeneration method of hydrogenation catalyst for preparing arylamine antioxidant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910146267.4A CN109701669B (en) | 2019-02-27 | 2019-02-27 | Regeneration method of hydrogenation catalyst for preparing arylamine antioxidant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109701669A CN109701669A (en) | 2019-05-03 |
| CN109701669B true CN109701669B (en) | 2021-06-25 |
Family
ID=66265340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910146267.4A Active CN109701669B (en) | 2019-02-27 | 2019-02-27 | Regeneration method of hydrogenation catalyst for preparing arylamine antioxidant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109701669B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112517024A (en) * | 2020-12-03 | 2021-03-19 | 安道麦安邦(江苏)有限公司 | Method for regenerating inactivated pirimiphos-methyl Raney nickel catalyst |
| CN113333033A (en) * | 2021-04-13 | 2021-09-03 | 青岛科技大学 | Regeneration method and application of supported ketoamine reduction alkylation catalyst |
| CN113333034A (en) * | 2021-04-13 | 2021-09-03 | 青岛科技大学 | Regeneration method and application of chloro-nitro-aromatic selective hydrogenation catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422740A (en) * | 2007-10-29 | 2009-05-06 | 新疆大学 | Activation method of inactive Pd/C catalyst in hydrogenation reaction |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN106732656A (en) * | 2016-12-27 | 2017-05-31 | 浙江新和成股份有限公司 | A kind of biotin intermediate is hydrogenated with the process for reactivation of palladium carbon catalyst |
| CN108927203A (en) * | 2018-10-12 | 2018-12-04 | 南京膜材料产业技术研究院有限公司 | A kind of regeneration method of phenol hydrogenation Pd@CN catalyst |
-
2019
- 2019-02-27 CN CN201910146267.4A patent/CN109701669B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422740A (en) * | 2007-10-29 | 2009-05-06 | 新疆大学 | Activation method of inactive Pd/C catalyst in hydrogenation reaction |
| CN103816923A (en) * | 2012-11-16 | 2014-05-28 | 万华化学集团股份有限公司 | Method for regenerating ruthenium hydrogenation catalyst |
| CN103816923B (en) * | 2012-11-16 | 2016-01-20 | 万华化学集团股份有限公司 | A kind of method of ruthenium hydrogenation catalyst regeneration |
| CN106732656A (en) * | 2016-12-27 | 2017-05-31 | 浙江新和成股份有限公司 | A kind of biotin intermediate is hydrogenated with the process for reactivation of palladium carbon catalyst |
| CN108927203A (en) * | 2018-10-12 | 2018-12-04 | 南京膜材料产业技术研究院有限公司 | A kind of regeneration method of phenol hydrogenation Pd@CN catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109701669A (en) | 2019-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109701669B (en) | Regeneration method of hydrogenation catalyst for preparing arylamine antioxidant | |
| CN103816923B (en) | A kind of method of ruthenium hydrogenation catalyst regeneration | |
| Poreddy et al. | Silver nanoparticles supported on alumina–a highly efficient and selective nanocatalyst for imine reduction | |
| CZ20004297A3 (en) | Process for preparing 4-aminodiphenylamines | |
| CN103357407A (en) | Preparation method and application of catalyst for one-step preparation of p-aminophenol from nitrobenzene | |
| CN105435815A (en) | Regeneration method of catalyst for preparing o-methylcyclohexanol | |
| CN110743544A (en) | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| CN114054061B (en) | Nitrogen-doped carbon-supported palladium catalyst and preparation method and application thereof | |
| CN106513028B (en) | A kind of catalyst and preparation method thereof and the application in reduction nitro compound | |
| CN115254167B (en) | Preparation method of N, S Co-doped mesoporous carbon supported Co catalyst and application thereof in hydrogenation | |
| CN101767016A (en) | Aromatic aldehyde selective hydrogenation catalyst for refining terephthalic acid | |
| CN102516222B (en) | Method for preparing cyclohexyl crown ether by catalytic hydrogenation of carbon supported ruthenium catalyst | |
| CN113797947A (en) | C-modified platinum-based catalyst and preparation method and application thereof | |
| Ruiz-Varilla et al. | Water-soluble NHC-stabilized platinum nanoparticles as recoverable catalysts for hydrogenation in water | |
| CN103846100A (en) | Pd/C-SiC catalyst for p-phthalic acid hydrorefining, preparation method and application thereof | |
| CN109438153B (en) | Method for preparing 2, 6-dimethyl-2-heptene through citronellal selective decarbonylation reaction | |
| CN103028422B (en) | Regeneration method for refining palladium-carbon catalysts through coarse terephthalic acid hydrogenation | |
| CN109529880B (en) | Catalyst regeneration method | |
| CN109201046B (en) | Preparation method and application of kettle residue tar-based mesoporous carbon-supported noble metal catalyst | |
| CN107245066B (en) | A kind of method that selectivity prepares chaff amine or tetrahydrofurfuryl amine | |
| CN101337895B (en) | Method for preparing 2,2'-di(trifluoromethyl)-4,4'-benzidine | |
| CN111545239B (en) | Solid catalyst for glycerol oxidation and preparation method thereof | |
| CN104741148B (en) | Method for preparing 3-chlorine-4 fluoronitrobenzene hydrogenation catalyst | |
| CN103657683A (en) | Regeneration method of Pt/C catalyst | |
| CN109734606B (en) | Method for prolonging service life of hydrogenation catalyst for preparing arylamine antioxidant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |