CN101357333B - Pd/C catalyst for preparing alcohol ether carboxylate and production method and use thereof - Google Patents
Pd/C catalyst for preparing alcohol ether carboxylate and production method and use thereof Download PDFInfo
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Abstract
A Pd/C catalyst for preparing alcohol ether carboxylate comprises the following components by weight percentages: 1-10% of palladium, 1-10% of alkaline earth metals, 1-10% of transition metals and 70-97% of active carbon. The Pd/C catalyst has the advantages that alkaline earth metal atoms and transition metal atoms are added to a palladium carbon catalyst, the dosage of the noble metal palladium is reduced, the catalyst property is improved, the catalytic activity is good, the selectivity is high, and the catalyst can increase the yield of the alcohol ether carboxylate by 10-20%.
Description
Technical field
The present invention relates to a kind of Pd/C catalyst and method for making and application, specifically a kind ofly be used for modification Pd/carbon catalyst and preparation method and the application that the catalytic oxidation AEO prepares alcohol ether carboxylate.
Background technology
Fatty Alcohol Ether Carboxylate (Alcohol Ether Carboxylate is the important anion surfactant of a class AEC), and its chemical constitution can be expressed as:
R (CH
2CH
2O)
nOCH
2The COOH acid type
R (CH
2CH
2O)
nOCH
2COOM salt type
In the formula, R is the open chain alkyl or cycloalkyl, and n is the integer greater than 1, M=Na
+, K
+, Li
+Fatty Alcohol Ether Carboxylate on chemical constitution the spitting image of soap, only between hydrophobic group and hydrophilic group, embedded polyoxyethylene groups, because the variation on the chemical constitution, not only had the water-soluble and stability in hard water that soap hardly matches, also possessed various good surface-actives and practical application performance.And a certain surface characteristic of product can regulate by the length that changes the hydrophobic group chain, adduction number and the pH value of EO, and the acid product is the nonionic characteristic, fully the then apparent anion characteristic of Zhong He salt formula product.AEC can not only same anion, nonionic, zwitterionic surfactant carry out composite; can also carry out composite with cationic surfactant or polymer; this is the not available characteristic of general anion surfactant, so it all is widely used on cosmetics and individual's protection articles for use, fiber industry, plastics industry, paper industry, leather industry and petroleum industry.
The external at present preparation technology about alcohol ether carboxylate mainly contains carboxy methylation method and precious metal catalyst oxidizing process two lines, and domestic research mainly is the carboxy methylation method.
The carboxy methylation method is the main method of producing AEC in the world at present, and promptly adopting monoxone or its salt is that the carboxy methylation agent is carried out carboxymethylation reaction to alkyl ether under alkali condition.System viscosity is very big in this technical process, and the engineering amplification ratio is difficulty, and conversion ratio is generally about 80%, produces by product sodium chloride, hydroxy acid sodium and unreacted sodium chloroacetate simultaneously, uses a large amount of acid can produce environmental pollution when refining.
Catalytic oxidation end methylol of AEO in the presence of noble metal catalyst is oxidized to carboxyl.Catalytic oxidation has eco-friendly characteristics, have simultaneously technological process short, low for equipment requirements, can be used for serialization production and can be made into advantage such as high purity product, its core and key are to select the preparation appropriate catalyst.
Japan Kao company proposes the earliest with precious metal catalyst oxidation alcohol ether system AEC, and has applied for patent (JP 50/96516) in 1975.Apply for a patent successively again in the eighties, its research mainly at Pd/C and adding main group nonmetalloid for helping aspect the component, activity of such catalysts and selectivity ratios are higher.
Patent US5292940, the US5463114 of Germany Henkel company use the Pd/C catalyst, and mainly the preparation technology to carboxylate studies.
Adding alkaline-earth metal and transition metal in the Pd/C catalyst still is not reported aspect the catalyst performance for helping component to improve.
Summary of the invention
It is good to the purpose of this invention is to provide a kind of catalytic activity, and selectivity is high is used for palladium carbon catalyst and preparation method and the application that the AEO catalytic oxidation prepares alcohol ether carboxylate.
The mass percent of catalyst of the present invention consists of:
Palladium 1～10wt%
Alkaline-earth metal 1～10wt%
Transition metal 1～10wt%
Active carbon 70～97wt%
Aforesaid palladium mass percent composition is preferably in 3～5wt%, and alkaline-earth metal is preferably in 1～3wt%, and transition metal is preferably in 1～3wt%.
Aforesaid alkaline-earth metal is Sr or Ba.
Aforesaid transition metal is Ni, Co, Cu or La.
Aforesaid active carbon, particle diameter are 200～400nm, specific area＞1200m
2/ g.
The concrete preparation process of catalyst of the present invention is as follows:
Palladium bichloride, alkaline earth metal chloride, transition metal chloride and 5～10wt%HCl are made into mixed solution, mixed solution is slowly splashed in the deionized water that contains active carbon, stir, drip off and continue to stir 4～6h, regulate the pH value to pH=12～14 with the inorganic alkali solution of 5～10wt% again, slow then Dropwise 5～10wt% formalin, be warming up to 60～90 ℃ of reductase 12s 0～60 minute, and reduced to room temperature and filter, will precipitate with the deionized water washing to neutral, filter, sealing is preserved;
Palladium bichloride wherein: alkaline earth metal chloride: transition metal chloride: HCl is 0.2～0.5g: 0.2～0.5g: 0.1～0.6g: 6～10ml; The quality of active carbon and deionized water and volume ratio are 4.4～4.9g: 40～60ml; Mixed solution is 1: 5～15 with the mass ratio that contains the deionized water of active carbon; The quality of mixed solution and formalin and volume ratio are 15g: 1～2ml.
It is as follows that catalytic oxidation of the present invention prepares the concrete grammar of alcohol ether carboxylate:
Add alcohol ether, deionized water, inorganic base and catalyst in reactor, stir, be warming up to 50～90 ℃, aerating oxygen keeps reactor pressure to react 3～6h under 0.03～0.20MPa, filters out catalyst, obtains product;
Wherein the mass ratio of alcohol ether and deionized water is 1: 4～6; The mol ratio of alcohol ether and inorganic base is 1: 1～1.1; The catalyst addition be the palladium atomic mass account for the alcohol ether quality 0.1%～0.5%.
Aforesaid alcohol ether is AEO
6, AEO
7, AEO
8Or AEO
9
Aforesaid inorganic base is NaOH, KOH or NaHCO
3Deng.
The present invention compared with prior art has following advantage:
Catalyst of the present invention adds alkaline earth metal atom and transition metal atoms in palladium carbon catalyst, can reduce the consumption of precious metal palladium, improve the performance of catalyst simultaneously, catalytic activity is good, the selectivity height can improve the productive rate 10%～20% of alcohol ether carboxylate.
The specific embodiment
Embodiment one
Take by weighing the 0.25g palladium bichloride, with 10ml 5wt%HCl dissolving wiring solution-forming, (particle diameter is 200nm, specific area 1300m to take by weighing the 4.85g active carbon
2/ g), add the 40ml deionized water, after stirring metal chloride solutions is slowly splashed into, stir 4h, regulate the pH value to pH=12 with the NaOH solution of 5wt% again, slow then Dropwise 5 wt% formalin 10ml, be warming up to 60 ℃ of reduction 60 minutes, reduce to room temperature and filter, will precipitate with the deionized water washing to neutral, filter, sealing is preserved.(catalyst consists of Pd 3wt%, active carbon 97wt%)
In reactor, add AEO
950g, deionized water 200g, KOH3.9g and the above-mentioned catalyst 10g that makes stir, and are warming up to 50 ℃, and aerating oxygen keeps reactor pressure to react 6h under 0.03MPa, filters out catalyst, obtains product.AEC by analysis
9Productive rate is 68%.
Embodiment two
Take by weighing the 0.25g palladium bichloride, the 0.45g strontium chloride dissolves wiring solution-forming with 6ml 10wt%HCl, and (particle diameter is 400nm, specific area 1400m to take by weighing the 4.70g active carbon
2/ g), add the 60ml deionized water, after stirring metal chloride solutions is slowly splashed into, stir 6h, use the NaHCO of 10wt% again
3Solution is regulated the pH value to pH=14, slowly drips 10wt% formalin 5ml then, is warming up to 90 ℃ of reductase 12s 0 minute, reduces to room temperature and filters, and will precipitate with deionized water and wash to neutral, filters the sealing preservation.(catalyst consists of Pd3wt%, Sr3wt%, active carbon 94wt%)
In reactor, add AEO
950g, deionized water 300g, KOH3.8g and the above-mentioned catalyst 20g that makes stir, and are warming up to 90 ℃, and aerating oxygen keeps reactor pressure to react 3h under 0.20MPa, filters out catalyst, obtains product.AEC by analysis
9Productive rate is 81.%.
Embodiment three
Take by weighing the 0.25g palladium bichloride, the 0.61g nickel chloride, with 8ml 8wt%HCl dissolving wiring solution-forming, (particle diameter is 300nm, specific area 1300m to take by weighing the 4.70g active carbon
2/ g), add the 50ml deionized water, after stirring metal chloride solutions is slowly splashed into, stir 4h, use the Na of 8wt% again
2CO
3Solution is regulated the pH value to pH=12, slowly drips 8wt% formalin 7ml then, is warming up to 70 ℃ of reduction 40 minutes, reduces to room temperature and filters, and will precipitate with deionized water and wash to neutral, filters the sealing preservation.(catalyst consists of Pd 3wt%, Ni3wt%, active carbon 94wt%)
In reactor, add AEO
650g, deionized water 250g, NaHCO
34.1g, stir with the above-mentioned catalyst 15g that makes, be warming up to 70 ℃, aerating oxygen keeps reactor pressure to react 5h under 0.07MPa, filters out catalyst, obtains product.AEC by analysis
6Productive rate is 70.7%.
Embodiment four
Take by weighing the 0.42g palladium bichloride, the 0.27g barium chloride, the 0.13g lanthanum chloride, with 7ml 8wt%HCl dissolving wiring solution-forming, (particle diameter is 300nm, specific area 1400m to take by weighing the 4.55g active carbon
2/ g), add the 50ml deionized water, after stirring metal chloride solutions is slowly splashed into, stir 5h, use the NH of 5wt% again
4OH solution is regulated the pH value to pH=12, slowly drips 8wt% formalin 7ml then, is warming up to 80 ℃ of reduction 30 minutes, reduces to room temperature and filters, and will precipitate with deionized water and wash to neutral, filters the sealing preservation.(catalyst consists of Pd5wt%, Ba3wt%, La1wt%, active carbon 91wt%)
In reactor, add AEO
750g, deionized water 200g, NaOH4.0g and the above-mentioned catalyst 10g that makes stir, and are warming up to 80 ℃, and aerating oxygen keeps reactor pressure to react 5h under 0.10MPa, filters out catalyst, obtains product.The AEC productive rate is 72.2% by analysis.
Embodiment five
Take by weighing the 0.42g palladium bichloride, the 0.45g strontium chloride, the 0.27g lanthanum chloride, with 10ml 5wt%HCl dissolving wiring solution-forming, (particle diameter is 250nm, specific area 1300m to take by weighing the 4.5g active carbon
2/ g), add the 40ml deionized water, after stirring metal chloride solutions is slowly splashed into, stir 4h, use the KHCO of 5wt% again
3Solution is regulated the pH value to pH=14, slowly drips 8wt% formalin 6ml then, is warming up to 60 ℃ of reduction 40 minutes, reduces to room temperature and filters, and will precipitate with deionized water and wash to neutral, filters the sealing preservation.(catalyst consists of Pd5wt%, Sr3wt%, La2wt%, active carbon 90wt%)
In reactor, add AEO
850g, deionized water 300g, KOH3.8g and the above-mentioned catalyst 15g that makes stir, and are warming up to 80 ℃, and aerating oxygen keeps reactor pressure to react 3h under 0.15MPa, filters out catalyst, obtains product.The AEC productive rate is 74.7% by analysis.
Embodiment six
Take by weighing the 0.25g palladium bichloride, the 0.41g cobalt chloride, with 10ml 5wt%HCl dissolving wiring solution-forming, (particle diameter is 250nm, specific area 1300m to take by weighing the 4.75g active carbon
2/ g), add the 50ml deionized water, after stirring metal chloride solutions is slowly splashed into, stir 4h, use the Na of 5wt% again
2CO
3Solution is regulated the pH value to pH=14, slowly drips 8wt% formalin 6ml then, is warming up to 60 ℃ of reduction 40 minutes, reduces to room temperature and filters, and will precipitate with deionized water and wash to neutral, filters the sealing preservation.(catalyst consists of Pd3wt%, Co2wt%, active carbon 95wt%)
In reactor, add AEO
850g, deionized water 300g, NH
4OH3.8g and the above-mentioned catalyst 15g that makes stir, and are warming up to 80 ℃, and aerating oxygen keeps reactor pressure to react 6h under 0.17MPa, filters out catalyst, obtains product.The AEC productive rate is 73% by analysis.
Embodiment seven
Take by weighing the 0.42g palladium bichloride, the 0.41g copper chloride, with 10ml 5wt%HCl dissolving wiring solution-forming, (particle diameter is 250nm, specific area 1300m to take by weighing the 4.6g active carbon
2/ g), add the 50ml deionized water, after stirring metal chloride solutions is slowly splashed into, stir 4h, use the NH of 5wt% again
4OH solution is regulated the pH value to pH=14, slowly drips 8wt% formalin 6ml then, is warming up to 60 ℃ of reduction 40 minutes, reduces to room temperature and filters, and will precipitate with deionized water and wash to neutral, filters the sealing preservation.(catalyst consists of Pd5wt%, Cu3wt%, active carbon 92wt%)
In reactor, add AEO
950g, deionized water 300g, NaHCO
33.6g, stir with the above-mentioned catalyst 15g that makes, be warming up to 80 ℃, aerating oxygen keeps reactor pressure to react 6h under 0.17MPa, filters out catalyst, obtains product.The AEC productive rate is 88.6% by analysis.
Embodiment eight
Take by weighing the 0.42g palladium bichloride, the 0.41g copper chloride, the 0.27g lanthanum chloride, with 10ml 5wt%HCl dissolving wiring solution-forming, (particle diameter is 250nm, specific area 1300m to take by weighing the 4.5g active carbon
2/ g), add the 50ml deionized water, after stirring metal chloride solutions is slowly splashed into, stir 4h, regulate the pH value to pH=14 with the KOH solution of 5wt% again, slowly drip 8wt% formalin 6ml then, be warming up to 60 ℃ of reduction 40 minutes, reduce to room temperature and filter, will precipitate with the deionized water washing to neutral, filter, sealing is preserved.(catalyst consists of Pd5wt%, Cu3wt%, La wt2%, active carbon 90wt%)
In reactor, add AEO
950g, deionized water 200g, NaHCO
33.6g, stir with the above-mentioned catalyst 10g that makes, be warming up to 80 ℃, aerating oxygen keeps reactor pressure to react 6h under 0.17MPa, filters out catalyst, obtains product.The AEC productive rate is 91.2% by analysis.
Claims (8)
1. Pd/C catalyst that is used to prepare alcohol ether carboxylate is characterized in that the mass percent of catalyst consists of:
Palladium 1～10wt%
Alkaline-earth metal 1～10wt%
Transition metal 1～10wt%
Active carbon 70～97wt%
Described transition metal is Ni, Co, Cu or La.
2. a kind of Pd/C catalyst that is used to prepare alcohol ether carboxylate as claimed in claim 1 is characterized in that described palladium mass percent is 3～5wt%, and alkaline-earth metal is 1～3wt%, and transition metal is 1～3wt%.
3. a kind of Pd/C catalyst that is used to prepare alcohol ether carboxylate as claimed in claim 1 is characterized in that described alkaline-earth metal is Sr or Ba.
4. a kind of Pd/C catalyst that is used to prepare alcohol ether carboxylate as claimed in claim 1 is characterized in that described active carbon, and particle diameter is 200～400nm, specific area＞1200m
2/ g.
5. as each described a kind of Pd/C Preparation of catalysts method that is used to prepare alcohol ether carboxylate of claim 1-4, it is characterized in that comprising the steps:
Palladium bichloride, alkaline earth metal chloride, transition metal chloride and 5～10wt%HCl are made into mixed solution, mixed solution is slowly splashed in the deionized water that contains active carbon, stir, drip off and continue to stir 4～6h, regulate the pH value to pH=12～14 with the inorganic alkali solution of 5～10wt% again, slow then Dropwise 5～10wt% formalin, be warming up to 60～90 ℃ of reductase 12s 0～60 minute, and reduced to room temperature and filter, will precipitate with the deionized water washing to neutral, filter, sealing is preserved;
Palladium bichloride wherein: alkaline earth metal chloride: transition metal chloride: HCl is 0.2～0.5g: 0.2～0.5g: 0.1～0.6g: 6～10ml; The quality of active carbon and deionized water and volume ratio are 4.4～4.9g: 40～60ml; Mixed solution is 1: 5～15 with the mass ratio that contains the deionized water of active carbon; The quality of mixed solution and formalin and volume ratio are 15g: 1～2ml.
6. as each described a kind of Pd/C Application of Catalyst that is used to prepare alcohol ether carboxylate of claim 1-4, it is characterized in that comprising the steps:
Add alcohol ether, deionized water, inorganic base and catalyst in reactor, stir, be warming up to 50～90 ℃, aerating oxygen keeps reactor pressure to react 3～6h under 0.03～0.20MPa, filters out catalyst, obtains product;
Wherein the mass ratio of alcohol ether and deionized water is 1: 4～6; The mol ratio of alcohol ether and inorganic base is 1: 1～1.1; The catalyst addition be the palladium atomic mass account for the alcohol ether quality 0.1%～0.5%.
7. a kind of Pd/C Application of Catalyst that is used to prepare alcohol ether carboxylate as claimed in claim 6 is characterized in that described alcohol ether is AEO
6, AEO
7, AEO
8Or AEO
9
8. a kind of Pd/C Application of Catalyst that is used to prepare alcohol ether carboxylate as claimed in claim 6 is characterized in that described inorganic base is NaOH, KOH or NaHCO
3
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| CN101905158B (en) * | 2010-07-21 | 2013-04-17 | 中国日用化学工业研究院 | Platinum carbon catalyst for preparing alcohol ether carboxylic acid and preparation method and application thereof |
| CN103301852A (en) * | 2013-06-07 | 2013-09-18 | 苏州市泰力达科技有限公司 | Preparation method of palladium-carbon catalyst |
| CN104549255B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | palladium-carbon catalyst and preparation method thereof |
| CN107848937B (en) | 2015-05-18 | 2024-03-29 | 罗地亚经营管理公司 | Method for oxidizing alcohols using an oxygen-containing gas |
| CN107051472B (en) * | 2017-04-19 | 2018-02-13 | 威莱(广州)日用品有限公司 | A kind of composite catalyst and its preparation and application for being used to prepare alcohol ether carboxylate |
| CN107321686B (en) * | 2017-06-05 | 2021-03-23 | 深圳市航盛新材料技术有限公司 | Cleaning method and cleaning solution for aluminum-air battery catalyst |
| CN109053429B (en) * | 2018-05-31 | 2021-05-14 | 上海发凯化工有限公司 | Preparation method of fatty alcohol ether carboxylic acid |
| CN110423340A (en) * | 2019-06-17 | 2019-11-08 | 南京先进生物材料与过程装备研究院有限公司 | A kind of method and reaction unit using micro flow field reaction technology preparation high-quality polyether carboxylation |
| CN110665500B (en) * | 2019-09-23 | 2022-08-05 | 广州米奇化工有限公司 | Composite catalyst and preparation method of alcohol ether carboxylate |
| CN112679335B (en) * | 2019-10-17 | 2023-04-07 | 中国石油化工股份有限公司 | System and method for preparing fatty alcohol polyether carboxylic acid through catalytic oxidation |
| CN114890891B (en) * | 2022-05-25 | 2023-11-24 | 辽宁华星日化产业技术研究院有限公司 | Preparation method of fatty alcohol polyoxyethylene ether carboxylate |
| CN115869942A (en) * | 2022-11-17 | 2023-03-31 | 利尔化学股份有限公司 | Modified palladium-carbon catalyst and preparation method and application thereof |
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