CN114345325A - Reactivation method of palladium/carbon catalyst - Google Patents
Reactivation method of palladium/carbon catalyst Download PDFInfo
- Publication number
- CN114345325A CN114345325A CN202111673516.9A CN202111673516A CN114345325A CN 114345325 A CN114345325 A CN 114345325A CN 202111673516 A CN202111673516 A CN 202111673516A CN 114345325 A CN114345325 A CN 114345325A
- Authority
- CN
- China
- Prior art keywords
- palladium
- carbon catalyst
- catalyst
- filter cake
- water
- 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.)
- Granted
Links
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
- Catalysts (AREA)
Abstract
The invention provides a reactivation method of a palladium/carbon catalyst, and relates to the technical field of catalyst regeneration. The method comprises the steps of firstly carrying out ultrasonic cleaning on a palladium/carbon catalyst, removing organic substances and inorganic salts attached to the palladium/carbon catalyst, and releasing part of active sites; then, stirring and washing by adopting a nitric acid solution to further activate the carrier carbon; and finally, adding ammonia water and copper chloride to generate a copper complex, and reducing copper by using hydrazine hydrate, so that the copper is loaded on the palladium/carbon catalyst in a simple substance form, and the copper is used as an auxiliary agent, thereby being beneficial to improving the activity of the palladium/carbon catalyst and enabling the performance of the activated palladium/carbon catalyst to basically reach the performance of the original catalyst. The activation method of the invention does not need to leach palladium, can reduce the loss of palladium in the recovery process, and is environment-friendly. In addition, by adopting the activation method, the activated palladium/carbon catalyst can be recycled for three times, thereby greatly reducing the production cost.
Description
Technical Field
The invention relates to the technical field of catalyst regeneration, in particular to a reactivation method of a palladium/carbon catalyst.
Background
Palladium is a rare metal and palladium/carbon catalysts are more expensive. Proper treatment of the deactivated Pd/C catalyst to restore its activity and reuse Pd metal is one ideal target.
There are many treatments for deactivated palladium/carbon catalysts. Chinese patent CN89101887.5 discloses a method for reactivating a palladium/carbon catalyst: contacting the palladium/carbon catalyst with hot water at the temperature of 200-350 ℃ for 0.5-10 h, then contacting the catalyst with cold water at the temperature of 100 ℃ for 0.5-10 h, and finally contacting the catalyst with concentrated alkaline solution for 1-10 h to complete the reactivation process. Such treatment methods are suitable for palladium-on-carbon catalysts having a low degree of deactivation.
Chinese patent CN103623843A discloses a method of washing with methanol, water and alkali, but it cannot fundamentally solve the problems of oxidation of part of palladium and complex formation, and the regenerated catalyst efficiency is also reduced.
For the palladium/carbon catalyst which is deactivated to a greater extent or completely, a method of extracting palladium from the catalyst is generally employed. Chinese patent CN95104435.4 discloses a method for recovering palladium from a palladium/carbon catalyst with a high degree of deactivation: the palladium/carbon catalyst is put into a roasting furnace for oxidizing roasting, roasting ash is acid-boiled by sulfuric acid solution to remove impurities, the ash after impurity removal is leached by a chlorination method to obtain palladium sponge, the leachate is further subjected to impurity removal by cation exchange resin exchange, and the exchange solution is purified by ammonia complexation and reduced to obtain the palladium sponge.
Disclosure of Invention
The invention aims to provide a method for reactivating a palladium/carbon catalyst, which is suitable for both the palladium/carbon catalyst with shallow inactivation degree and the palladium/carbon catalyst with heavier inactivation degree, has simple process and environmental protection, can reduce the loss of palladium in the recovery process, and the performance of the activated palladium/carbon catalyst can basically reach the performance of the original catalyst.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a reactivation method of a palladium/carbon catalyst, which comprises the following steps:
putting a palladium/carbon catalyst into a mixed solvent for ultrasonic cleaning, and separating to obtain a first filter cake; the mixed solvent is a mixed solvent of water and liquid amide;
mixing the first filter cake with a nitric acid solution, performing agitation washing, and separating to obtain a second filter cake;
and mixing the second filter cake, ammonia water and copper chloride, and then adding hydrazine hydrate into the obtained mixed feed liquid for reduction to obtain the activated palladium/carbon catalyst.
Preferably, the mass ratio of the mixed solvent to the palladium/carbon catalyst is 1-2: 1.
Preferably, the mass ratio of water to liquid amide in the mixed solvent is 1-3: 1; the liquid amide includes N, N-dimethylformamide or N, N-dimethylformamide.
Preferably, the ultrasonic cleaning temperature is 80-90 ℃, the ultrasonic frequency is 40-60 HZ, and the ultrasonic time is 0.5-1 h.
Preferably, the mass fraction of the nitric acid solution is 3-5%, and the mass ratio of the nitric acid solution to the palladium/carbon catalyst is 1-3: 1.
Preferably, the mass concentration of the ammonia water is 3-5%, and the mass ratio of the ammonia water to the palladium/carbon catalyst is 1-1.5: 1.
Preferably, the mass ratio of the copper chloride to the palladium/carbon catalyst dry weight is 1: 150 to 180.
Preferably, the mass ratio of the hydrazine hydrate to the dry weight of the palladium/carbon catalyst is 1: 20 to 30.
Preferably, the mixing time of the second filter cake, ammonia water and copper chloride is 1-2 hours, and the temperature is 50-60 ℃.
Preferably, the reduction temperature is 70-80 ℃, and the heat preservation time is 5-6 h.
The invention provides a reactivation method of a palladium/carbon catalyst, which comprises the following steps: putting a palladium/carbon catalyst into a mixed solvent for ultrasonic cleaning, and separating to obtain a first filter cake; the mixed solvent is a mixed solvent of water and liquid amide; mixing the first filter cake with a nitric acid solution, performing agitation washing, and separating to obtain a second filter cake; and mixing the second filter cake, ammonia water and copper chloride, and then adding hydrazine hydrate into the obtained mixed feed liquid for reduction to obtain the activated palladium/carbon catalyst.
The method comprises the steps of firstly carrying out ultrasonic cleaning on a palladium/carbon catalyst, removing organic substances and inorganic salts attached to the palladium/carbon catalyst, and releasing part of active sites; then, stirring and washing by adopting a nitric acid solution to further activate the carrier carbon; and finally, adding ammonia water and copper chloride to generate a copper complex, and reducing copper by using hydrazine hydrate, so that the copper is loaded on the palladium/carbon catalyst in a simple substance form, and the copper is used as an auxiliary agent, thereby being beneficial to improving the activity of the palladium/carbon catalyst and enabling the performance of the activated palladium/carbon catalyst to basically reach the performance of the original catalyst.
The activation method of the invention does not need to leach palladium, can reduce the loss of palladium in the recovery process, and is environment-friendly. In addition, by adopting the activation method, the activated palladium/carbon catalyst can be recycled for three times, thereby greatly reducing the production cost.
Detailed Description
The invention provides a reactivation method of a palladium/carbon catalyst, which comprises the following steps:
putting a palladium/carbon catalyst into a mixed solvent for ultrasonic cleaning, and separating to obtain a first filter cake; the mixed solvent is a mixed solvent of water and liquid amide;
mixing the first filter cake with a nitric acid solution, performing agitation washing, and separating to obtain a second filter cake;
and mixing the second filter cake, ammonia water and copper chloride, and then adding hydrazine hydrate into the obtained mixed feed liquid for reduction to obtain the activated palladium/carbon catalyst.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
The method comprises the steps of placing a palladium/carbon catalyst in a mixed solvent for ultrasonic cleaning, and separating to obtain a first filter cake. In the present invention, the palladium/carbon catalyst is preferably a BPDA (2,3,3',4' -biphenyltetracarboxylic dianhydride) coupled palladium/carbon catalyst. In the present invention, the palladium/carbon catalyst is preferably an incompletely deactivated catalyst. In the present invention, the moisture content of the palladium/carbon catalyst is preferably 60 to 70 wt.%; in the present invention, the mass of the palladium/carbon catalyst described later is referred to as the wet weight of the palladium/carbon catalyst, unless otherwise specified. The invention has no special requirement on the loading amount of palladium in the palladium/carbon catalyst, and in the embodiment of the invention, the mass content of palladium in the palladium/carbon catalyst is 5%.
In the invention, the mass ratio of water to liquid amide in the mixed solvent is preferably 1-3: 1, and more preferably 1.5-2.5: 1; the liquid amide preferably comprises N, N-dimethylformamide or N, N-dimethylformamide.
In the present invention, the mass ratio of the mixed solvent to the palladium/carbon catalyst is preferably 1 to 2:1, and more preferably 1.2 to 1.8: 1.
In the invention, the ultrasonic cleaning temperature is preferably 80-90 ℃, and more preferably 83-88 ℃; the ultrasonic frequency is preferably 40-60 HZ, and more preferably 45-55 HZ; the ultrasonic time is preferably 0.5-1 h.
The invention removes organic matters and inorganic salts attached to the palladium/carbon catalyst by ultrasonic cleaning, and releases partial active sites.
After the ultrasonic cleaning is completed, the obtained mixture is separated by the invention. The present invention has no special requirement on the separation mode, and the solid-liquid separation mode known in the field can be adopted, such as filtration.
After isolation the present invention preferably further comprises washing the resulting solid to obtain a first filter cake. In the present invention, the washing liquid used for the washing is preferably water. The washing frequency is preferably 3 times, and the total water consumption and the mass ratio of the palladium/carbon catalyst in 3 times are preferably 2-3: 1. The invention has no special requirement on the water consumption of each washing, and the water is preferably evenly distributed.
After the first filter cake is obtained, the first filter cake is mixed with nitric acid solution, stirred and washed, and separated to obtain a second filter cake.
In the invention, the mass fraction of the nitric acid solution is preferably 3-5%, and the mass ratio of the nitric acid solution to the palladium/carbon catalyst is preferably 1-3: 1, more preferably 1.5-2.5: 1.
in the invention, the temperature of the agitation washing is preferably 40-50 ℃ and the time is 2-3 h. The present invention has no particular requirement on the rate of said whisking, as long as the agitation rate is well known in the art.
The invention utilizes nitric acid solution to stir and wash the carbon carrier further.
After the stirring is completed, the invention separates the obtained mixture. The present invention has no special requirement on the separation mode, and the solid-liquid separation mode known in the field can be adopted, such as filtration.
After isolation the present invention preferably further comprises washing the resulting solid to obtain a second filter cake. In the present invention, the washing liquid used for the washing is preferably water. The washing frequency is preferably 4 times, and the total water consumption and the mass ratio of the palladium/carbon catalyst for 4 times are preferably 2-3: 1. The invention has no special requirement on the water consumption of each washing, and the water is preferably evenly distributed.
After the second filter cake is obtained, the second filter cake, ammonia water and copper chloride are mixed, and then hydrazine hydrate is added into the obtained mixed feed liquid for reduction, so that the activated palladium/carbon catalyst is obtained.
In the invention, the mass concentration of the ammonia water is preferably 3-5%, and the mass ratio of the ammonia water to the palladium/carbon catalyst is preferably 1-1.5: 1; the mass ratio of copper chloride to palladium/carbon catalyst dry weight is preferably 1: 150 to 180, more preferably 1:160 to 170.
In the present invention, mixing the second filter cake, aqueous ammonia, and copper chloride preferably comprises: the ammonia water and the second filter cake are firstly mixed, and then the copper chloride is added for second mixing under the stirring condition. The stirring rate in the mixing process is not particularly required in the present invention, and the stirring rate well known in the art can be adopted.
In the invention, the mixing time is preferably 1-2 h (namely the stirring and mixing time after adding the copper chloride); the mixing temperature is preferably 50-60 ℃. In the process of mixing the ammonia water and the copper chloride, the ammonia water and the copper chloride generate a complex compound to be attached to the surface of the palladium/carbon catalyst.
In the present invention, the mass ratio of the hydrazine hydrate to the dry weight of the palladium/carbon catalyst is preferably 1: 20 to 30, and more preferably 1:22 to 28.
In the invention, the reduction temperature is preferably 70-80 ℃, and the heat preservation time is preferably 5-6 h. In the reduction process, the hydrazine hydrate reduces the complex of copper into a copper simple substance, and the copper simple substance is used as an auxiliary agent to improve the activity of the palladium/carbon catalyst, so that the performance of the activated palladium/carbon catalyst can basically reach the performance of the original catalyst.
After the reduction is completed, the invention preferably further comprises the step of sequentially carrying out solid-liquid separation and water washing on the product obtained by the reduction to obtain the activated palladium/carbon catalyst.
The invention has no special requirement on the solid-liquid separation mode, and the solid-liquid separation mode which is well known in the field, such as filtration, can be adopted. The invention has no special requirements on the washing process, and the washing process well known in the field can be adopted.
The method for reactivating the palladium/carbon catalyst of the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
The mass content of palladium in the new palladium/carbon catalyst is 5 percent, and the new palladium/carbon catalyst is used for coupling reaction of BPDA; the coupling reaction of the BPDA takes 4-chlorophthalic anhydride as a raw material and palladium/carbon as a catalyst, the coupling reaction is carried out in the presence of sodium hydroxide and a reducing agent hydroxylamine sulfate, the filtrate is acidified after filtration to obtain the BPTA, and the yield of the BPTA is 85.6%. The non-activated palladium-on-carbon catalysts used in example 1, comparative example 1, and comparative examples 4-5 were the same batch of palladium-on-carbon catalysts.
Example 1: for the first time
Taking 50g of palladium/carbon catalyst which contains 65.3 wt.% of moisture and is used in a workshop, adding 80g of mixed solvent (the mass ratio of water to DMF is 2:1), heating to 83 ℃, carrying out ultrasonic treatment for 45min at the ultrasonic frequency of 55HZ, filtering, and washing with 150g of water for 3 times; mixing and stirring the filter cake and 100g of nitric acid solution with the mass fraction of 4%, heating to 45 ℃, preserving heat for 3 hours, filtering, and washing the filter cake with 125g of water for four times; mixing and stirring the filter cake and 75g of ammonia water with the mass concentration of 3%, adding 0.0975g of copper chloride, preserving the heat at 55 ℃ for 1h, adding 0.6196g of hydrazine hydrate, reducing at 75 ℃ for 6h, filtering and washing with water to obtain an activated palladium/carbon catalyst, and applying the activated palladium/carbon catalyst to coupling reaction of BPDA, wherein the yield of BPTA can reach 85.5%.
Example 2: for the second time
Taking 50g of palladium/carbon catalyst which contains 66.7 wt.% of moisture and is used for one time, adding 90g of mixed solvent (the mass ratio of water to DMF is 1:1), heating to 85 ℃, carrying out ultrasonic treatment for 1h at the ultrasonic frequency of 45HZ, filtering, and washing with 150g of water for 3 times; mixing and stirring the filter cake and 125g of nitric acid solution with the mass fraction of 3%, heating to 48 ℃, preserving heat for 3 hours, filtering, and washing the filter cake with 150g of water for four times; mixing and stirring the filter cake and 50g of ammonia water with the mass concentration of 5%, adding 0.1009g of copper chloride, preserving the heat at 58 ℃ for 1h, adding 0.6578g of hydrazine hydrate, reducing at 70 ℃ for 6h, filtering and washing with water to obtain an activated palladium/carbon catalyst, and applying the activated palladium/carbon catalyst to coupling reaction of BPDA, wherein the yield of BPTA can reach 84.8%.
Example 3: for the third time
Taking 50g of palladium/carbon catalyst containing 64.6 wt.% of moisture after the second use, adding 90g of mixed solvent (the mass ratio of water to DMF is 1:1), heating to 85 ℃, carrying out ultrasonic treatment for 1h at the ultrasonic frequency of 45HZ, filtering, and washing with 150g of water for 3 times; mixing and stirring the filter cake and 125g of nitric acid solution with the mass fraction of 3%, heating to 48 ℃, preserving heat for 3 hours, filtering, and washing the filter cake with 150g of water for four times; mixing and stirring the filter cake and 50g of ammonia water with the mass concentration of 5%, adding 0.1009g of copper chloride, preserving the heat at 58 ℃ for 1h, adding 0.6578g of hydrazine hydrate, reducing at 70 ℃ for 6h, filtering and washing with water to obtain an activated palladium/carbon catalyst, and applying the activated palladium/carbon catalyst to coupling reaction of BPDA, wherein the yield of BPTA can reach 83.8%.
Comparative example 1: is not activated for the first time
The palladium/carbon catalyst without activation is used for coupling reaction of BPDA, and the yield of BPTA is 32.3%.
Comparative example 2: is not activated for the second time
The palladium/carbon catalyst after the first use is not activated and is used for coupling reaction of BPDA, and the yield of BPTA is 20.1%.
Comparative example 3: is not activated for the third time
The palladium/carbon catalyst used for the second time without activation is used for coupling reaction of BPDA, and the yield of BPTA is 10.2%.
Comparative example 4
Mixing 50g of palladium/carbon catalyst containing 65.3 wt.% of moisture used in a workshop and 100g of nitric acid solution with the mass fraction of 4%, stirring, heating to 45 ℃, preserving heat for 3 hours, filtering, and washing a filter cake by 125g of water for four times; mixing and stirring the filter cake and 75g of 3% ammonia water, adding 0.0975g of copper chloride, preserving heat at 55 ℃ for 1h, adding 0.6196g of hydrazine hydrate, preserving heat at 75 ℃ for 6h, filtering and washing with water to obtain an activated palladium/carbon catalyst, and applying the activated palladium/carbon catalyst to coupling reaction of BPDA, wherein the yield of BPTA is 54.3%.
Comparative example 5
Taking 50g of a 5% palladium/carbon catalyst which contains 65.3 wt.% of moisture and is used in a workshop, adding 80g of a mixed solvent (the mass ratio of water to DMF is 2:1), heating to 83 ℃, carrying out ultrasonic treatment for 45min at the ultrasonic frequency of 55HZ, filtering, and washing with 150g of water for 3 times; mixing and stirring the filter cake and 75g of ammonia water with the mass fraction of 3%, adding 0.0975g of copper chloride, preserving the heat at 55 ℃ for 1h, adding 0.6196g of hydrazine hydrate, reducing at 75 ℃ for 6h, filtering and washing with water to obtain an activated palladium/carbon catalyst, and applying the activated palladium/carbon catalyst to coupling reaction of BPDA, wherein the yield of BPTA can reach 65.4%.
Comparative example 6
Taking 50g of palladium/carbon catalyst which contains 65.3 wt.% of moisture and is used in a workshop, adding 80g of mixed solvent (the mass ratio of water to DMF is 2:1), heating to 83 ℃, carrying out ultrasonic treatment for 45min at the ultrasonic frequency of 55HZ, filtering, and washing with 150g of water for 3 times; mixing and stirring the filter cake and 100g of nitric acid solution with the mass fraction of 4%, heating to 45 ℃, preserving heat for 3 hours, filtering, and washing the filter cake with 125g of water for four times; the activated palladium/carbon catalyst was used for coupling reaction of BPDA with BPTA yield of 42.6%.
TABLE 1 comparison of Activity evaluation of reactivated Palladium on carbon catalyst and non-activated Palladium on carbon catalyst
| Palladium/carbon catalyst | Yield% |
| Novel catalyst | 85.6 |
| Example 1 | 85.5 |
| Example 2 | 84.8 |
| Example 3 | 83.8 |
| Comparative example 1 | 32.3 |
| Comparative example 2 | 20.1 |
| Comparative example 3 | 10.2 |
| Comparative example 4 | 54.3 |
| Comparative example 5 | 65.4 |
| Comparative example 6 | 42.6 |
From the results in table 1, it is understood that the activation of the palladium/carbon catalyst by the activation method of the present invention can substantially achieve the original catalyst performance, and can be repeatedly used for 3 times or more. In addition, from the results of example 1 and comparative examples 4 to 6, it is understood that the activation effect is reduced by omitting any of the three steps of ultrasonic cleaning, nitric acid solution agitation cleaning and addition of a copper assistant.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method of reactivating a palladium on carbon catalyst comprising the steps of:
putting a palladium/carbon catalyst into a mixed solvent for ultrasonic cleaning, and separating to obtain a first filter cake; the mixed solvent is a mixed solvent of water and liquid amide;
mixing the first filter cake with a nitric acid solution, performing agitation washing, and separating to obtain a second filter cake;
and mixing the second filter cake, ammonia water and copper chloride, and then adding hydrazine hydrate into the obtained mixed feed liquid for reduction to obtain the activated palladium/carbon catalyst.
2. The reactivation method according to claim 1, wherein a mass ratio of the mixed solvent to the palladium/carbon catalyst is 1 to 2: 1.
3. The reactivation method according to claim 1, wherein the mass ratio of water to liquid amide in the mixed solvent is 1 to 3: 1; the liquid amide includes N, N-dimethylformamide or N, N-dimethylformamide.
4. The reactivation method according to claim 1, wherein the temperature of the ultrasonic cleaning is 80-90 ℃, the ultrasonic frequency is 40-60 HZ, and the ultrasonic time is 0.5-1 h.
5. The reactivation method according to claim 1, wherein the mass fraction of the nitric acid solution is 3 to 5%, and the mass ratio of the nitric acid solution to the palladium/carbon catalyst is 1 to 3: 1.
6. The reactivation method according to claim 1, wherein the mass concentration of the aqueous ammonia is 3 to 5%, and the mass ratio of the aqueous ammonia to the palladium/carbon catalyst is 1 to 1.5: 1.
7. The reactivation process of claim 1, wherein the mass ratio of copper chloride to palladium/carbon catalyst dry weight is 1: 150 to 180.
8. The reactivation method according to claim 1, wherein the mass ratio of the hydrazine hydrate to the dry weight of the palladium/carbon catalyst is 1: 20 to 30.
9. The reactivation method of claim 1, wherein the second filter cake, the aqueous ammonia, and the cupric chloride are mixed for 1-2 hours at a temperature of 50-60 ℃.
10. The reactivation method according to claim 1, wherein the reduction temperature is 70 to 80 ℃ and the holding time is 5 to 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111673516.9A CN114345325B (en) | 2021-12-31 | 2021-12-31 | Reactivation method of palladium/carbon catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111673516.9A CN114345325B (en) | 2021-12-31 | 2021-12-31 | Reactivation method of palladium/carbon catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114345325A true CN114345325A (en) | 2022-04-15 |
| CN114345325B CN114345325B (en) | 2022-11-22 |
Family
ID=81106071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111673516.9A Active CN114345325B (en) | 2021-12-31 | 2021-12-31 | Reactivation method of palladium/carbon catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114345325B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116020451A (en) * | 2022-12-22 | 2023-04-28 | 雅邦绿色过程与新材料研究院南京有限公司 | Palladium-carbon catalyst regeneration activation method for removing N-benzyl by hydrogenation based on N-heterocyclic alkane compound |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3726915A (en) * | 1970-07-13 | 1973-04-10 | Standard Oil Co | Phthalic acid purification with copper activated palladium on carbon catalysts |
| JPH01299236A (en) * | 1988-05-26 | 1989-12-04 | Mitsubishi Kasei Corp | Regeneration of palladium carrying catalyst |
| US20020103080A1 (en) * | 2000-11-29 | 2002-08-01 | Council Of Scientific & Industrial Research | Process for the activation of a metallic palladium based catalyst useful for the direct oxidation of hydrogen to hydrogen peroxide |
| CN101024184A (en) * | 2007-03-16 | 2007-08-29 | 扬子石油化工股份有限公司 | Method for reactivating deactivated palladium/carbon catalyst |
| CN101024185A (en) * | 2007-03-16 | 2007-08-29 | 扬子石油化工股份有限公司 | Method for reactivating palledium/carbon catalyst |
| JP2011041919A (en) * | 2009-08-21 | 2011-03-03 | Tosoh Corp | Method of removing dissolved palladium |
| CN102191501A (en) * | 2010-03-10 | 2011-09-21 | 比亚迪股份有限公司 | Palladium remover and preparation method thereof, and plastic surface activation method |
| CN103028422A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Regeneration method for refining palladium-carbon catalysts through coarse terephthalic acid hydrogenation |
| CN103754883A (en) * | 2014-01-02 | 2014-04-30 | 河南科技大学 | Catalyst for transforming silicon tetrachloride into trichlorosilane through hydrodechlorination and preparation method of catalyst |
| CN104829550A (en) * | 2015-05-04 | 2015-08-12 | 四川大学 | Method for high-efficiency preparation of an o-hydroxyphenyl heterocyclic derivative through C-H/C-H oxidative coupling reaction based on transition metal catalysis |
| CN105107552A (en) * | 2015-09-07 | 2015-12-02 | 广西梧州通轩林产化学有限公司 | Reactivation method of palladium-carbon catalyst for preparation of disproportionated rosin |
| CN106084220A (en) * | 2016-06-22 | 2016-11-09 | 河北海力香料股份有限公司 | A kind of compositions of 3,3 ', 4,4 ' Biphenyl Ether dianhydrides and 9 oxygen (miscellaneous) fluorenes dianhydride and its preparation method and application |
| 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 |
| CN106861717A (en) * | 2017-03-14 | 2017-06-20 | 中国科学技术大学先进技术研究院 | A kind of CuPd metal nanos catalyst and preparation method thereof, application |
| CN109529880A (en) * | 2018-12-19 | 2019-03-29 | 浙江常山科润新材料有限公司 | A kind of regeneration method of catalyst |
| CN110090648A (en) * | 2019-04-30 | 2019-08-06 | 皖南医学院 | A kind of copper palladium oxide nano particle and its preparation method and application of redox graphene load |
| CN110743544A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof |
| CN111628178A (en) * | 2020-05-22 | 2020-09-04 | 西安交通大学 | Carbon-supported palladium copper tantalum nitride nano electro-catalyst for direct methanol and formic acid fuel cell and preparation method thereof |
-
2021
- 2021-12-31 CN CN202111673516.9A patent/CN114345325B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3726915A (en) * | 1970-07-13 | 1973-04-10 | Standard Oil Co | Phthalic acid purification with copper activated palladium on carbon catalysts |
| JPH01299236A (en) * | 1988-05-26 | 1989-12-04 | Mitsubishi Kasei Corp | Regeneration of palladium carrying catalyst |
| US20020103080A1 (en) * | 2000-11-29 | 2002-08-01 | Council Of Scientific & Industrial Research | Process for the activation of a metallic palladium based catalyst useful for the direct oxidation of hydrogen to hydrogen peroxide |
| CN101024184A (en) * | 2007-03-16 | 2007-08-29 | 扬子石油化工股份有限公司 | Method for reactivating deactivated palladium/carbon catalyst |
| CN101024185A (en) * | 2007-03-16 | 2007-08-29 | 扬子石油化工股份有限公司 | Method for reactivating palledium/carbon catalyst |
| JP2011041919A (en) * | 2009-08-21 | 2011-03-03 | Tosoh Corp | Method of removing dissolved palladium |
| CN102191501A (en) * | 2010-03-10 | 2011-09-21 | 比亚迪股份有限公司 | Palladium remover and preparation method thereof, and plastic surface activation method |
| CN103028422A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Regeneration method for refining palladium-carbon catalysts through coarse terephthalic acid hydrogenation |
| CN103754883A (en) * | 2014-01-02 | 2014-04-30 | 河南科技大学 | Catalyst for transforming silicon tetrachloride into trichlorosilane through hydrodechlorination and preparation method of catalyst |
| CN104829550A (en) * | 2015-05-04 | 2015-08-12 | 四川大学 | Method for high-efficiency preparation of an o-hydroxyphenyl heterocyclic derivative through C-H/C-H oxidative coupling reaction based on transition metal catalysis |
| CN105107552A (en) * | 2015-09-07 | 2015-12-02 | 广西梧州通轩林产化学有限公司 | Reactivation method of palladium-carbon catalyst for preparation of disproportionated rosin |
| CN106084220A (en) * | 2016-06-22 | 2016-11-09 | 河北海力香料股份有限公司 | A kind of compositions of 3,3 ', 4,4 ' Biphenyl Ether dianhydrides and 9 oxygen (miscellaneous) fluorenes dianhydride and its preparation method and application |
| 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 |
| CN106861717A (en) * | 2017-03-14 | 2017-06-20 | 中国科学技术大学先进技术研究院 | A kind of CuPd metal nanos catalyst and preparation method thereof, application |
| CN109529880A (en) * | 2018-12-19 | 2019-03-29 | 浙江常山科润新材料有限公司 | A kind of regeneration method of catalyst |
| CN110090648A (en) * | 2019-04-30 | 2019-08-06 | 皖南医学院 | A kind of copper palladium oxide nano particle and its preparation method and application of redox graphene load |
| CN110743544A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof |
| CN111628178A (en) * | 2020-05-22 | 2020-09-04 | 西安交通大学 | Carbon-supported palladium copper tantalum nitride nano electro-catalyst for direct methanol and formic acid fuel cell and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| R. MOHAN RAO ET AL.: ""Sequential coupling/desilylation–coupling/cyclization in a single pot under Pd/C–Cu catalysis: Synthesis of 2-(hetero)aryl indoles"", 《 ORG. BIOMOL. CHEM.》 * |
| 徐锋: ""钯碳催化剂失活原因分析及处理措施"", 《石油化工技术与经济》 * |
| 翟康等: ""对甲基苯乙酮催化加氢用钯炭催化剂研究"", 《工业催化》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116020451A (en) * | 2022-12-22 | 2023-04-28 | 雅邦绿色过程与新材料研究院南京有限公司 | Palladium-carbon catalyst regeneration activation method for removing N-benzyl by hydrogenation based on N-heterocyclic alkane compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114345325B (en) | 2022-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100453176C (en) | Method for reactivating deactivated palladium/carbon catalyst | |
| CN114345325B (en) | Reactivation method of palladium/carbon catalyst | |
| CN105080521A (en) | Activated carbon regeneration method | |
| CN113387851B (en) | Preparation method of 4, 4' -dichlorodiphenyl sulfone | |
| US4490297A (en) | Method for the recovery and reuse of cobalt and/or manganese components of catalysts | |
| CN112724009B (en) | Method for producing fumaric acid from maleic anhydride wastewater | |
| CN100423835C (en) | Method for reactivating palledium/carbon catalyst | |
| CN108554395B (en) | Regeneration method of inactivated activated carbon in acetaminophen refining stage | |
| CN109225312A (en) | A kind of synthetic method of methyl tosylate | |
| US3911020A (en) | Process for the preparation of dialkylbenzene dihydroperoxide | |
| CN116332747A (en) | Method for preparing biphenyl tetracarboxylic acid based on palladium-carbon catalyst and activation method of palladium-carbon catalyst | |
| RU2714201C1 (en) | Extraction of oxalic acid from industrial ferric oxalate | |
| CN107963986B (en) | Method for co-producing high-purity schofield salt and G salt | |
| CN111269196A (en) | Method for preparing NS by UHP oxidation | |
| JPS61106535A (en) | Recovery of benzoic acid | |
| JP7489428B2 (en) | Method for improving recovery rate of regenerated bis(2-hydroxyethyl) terephthalate | |
| JPH0235734B2 (en) | KOJUNDOPARAJIUMUSHIBOZOKUKARUBONSANENNOSEIZOHO | |
| JPH0611725B2 (en) | Method for producing succinic acid | |
| JPH1081693A (en) | Decarboxylation of 2-ketoaldonic acid | |
| US1545322A (en) | Regeneration of sugar-purifying reagents | |
| CN103121960B (en) | Efficient recrystallization method of tetraacetylethylenediamine | |
| TWI851923B (en) | Method for producing recycled polyester chips from recycled polyester fabric | |
| CN101391752B (en) | Method for purification of sodium bromate by energy-saving method | |
| CN116020451A (en) | Palladium-carbon catalyst regeneration activation method for removing N-benzyl by hydrogenation based on N-heterocyclic alkane compound | |
| JPS5843382B2 (en) | Processing method for liquid phase oxidation reaction residue |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230403 Address after: 050000, 200 meters east of the intersection of Industrial Street and Huahua North Road in the Circular Chemical Industry Park of Shijiazhuang City, Hebei Province Patentee after: Hebei Dongli New Material Co.,Ltd. Address before: 052165 No. 2 Jinsha Road, economic and Technological Development Zone, Shijiazhuang City, Hebei Province Patentee before: HEBEI HAILI FRAGRANCES CO.,LTD. |
|
| TR01 | Transfer of patent right |