CN1161252A - Noble metals hydrogenation catalyst of ruthenium/carbon loaded type, and method for preparing same - Google Patents
Noble metals hydrogenation catalyst of ruthenium/carbon loaded type, and method for preparing same Download PDFInfo
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- CN1161252A CN1161252A CN 97103653 CN97103653A CN1161252A CN 1161252 A CN1161252 A CN 1161252A CN 97103653 CN97103653 CN 97103653 CN 97103653 A CN97103653 A CN 97103653A CN 1161252 A CN1161252 A CN 1161252A
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Abstract
The present invention relates to a kind of noble metal hydrogenation catalyst for the medical trade, specially to a noble metal catalyst used in the alcoholic fluidizing state reaction when taking glucose as raw material to produce sorbierite. It is composed of activated carbon and metal ruthenium on the load activated carbon after activation treatment. The prepn. method consists of selecting the carbon carrier and conducting the reactivation treatment, prepn. of active component rubhenium, sedimentation of active component rubhenium salt on the carbon carrier and activation of catalyst. Compared with the traditional Rayleigh nickel catalyst, the reaction temp. can lower to 105 deg.C, the pressure lowers to 3MPa, and the consumption of catalyst is only 0.1 Kg, so the cost is lowered effectively and the productive efficiency is increased.
Description
A kind of noble metals hydrogenation catalyst of ruthenium/carbon loaded type and preparation method thereof, relate to a kind of a kind of noble metal hydrogenation catalyst that is used for chemical industry, pharmaceuticals industry, particularly a kind of is raw material used a kind of noble metal catalyst and preparation method thereof when producing the fluidized-bed reaction of sorbierite with glucose.
At present, produce sorbierite for the catalytic material hydrogenation, mostly adopt traditional Rayleigh nickel (skeleton nickel) to make catalyst with glucose.This reaction condition is relatively harsher, requires the temperature of reaction higher, and reaction pressure is big, reaches 15MPa.Produce the unit cost height of sorbierite, the consumption of catalyst is very big, produces the catalyst that sorbierite per ton approximately consumes 2kg.
Purpose of the present invention is exactly to use existing catalyst to carry out in the fluidized-bed reaction production sorbierite process as raw material with glucose in order to overcome, the severe reaction conditions that exists, the shortcoming that production cost is high provides a kind of novel noble metals hydrogenation catalyst of ruthenium/carbon loaded type that a kind of reaction condition is wide, catalyst consumption is low, production cost is low and preparation method thereof.
The objective of the invention is to be achieved through the following technical solutions.
A kind of noble metals hydrogenation catalyst of ruthenium/carbon loaded type is characterized in that: catalyst comprises by activated carbon and is carried on the activated carbon and the metal Ru of activated processing is formed that the content of ruthenium is: 4.8～5.3%, and all the other are activated carbon and unavoidable impurities, wherein
Cl
-＜1×10
-6M，
Fe＜1×10
-4M，
Pb＜1×10
-4M，
Cu＜1×10
-4M。
The specific area of catalyst activity carbon carrier is 600～1300m/g, and pore volume is 0.2～2.2ml/g, particle size distribution: 100%＜210 μ m.
The preparation method of a kind of noble metals hydrogenation catalyst of ruthenium/carbon loaded type of the present invention comprises the selection of carbon carrier and reactivation processing, the preparation of active constituent ruthenium, the deposition of active constituent ruthenium salt on carbon carrier, the activation processing of catalyst, it is characterized in that:
A. after selecting satisfactory activated carbon, be 1.013 * 10 in vacuum
-3～1.013 * 10
-4Pa, being warming up to temperature is 500～1200 ℃, further activates and intensive treatment under the condition in 10～30 hours at constant temperature;
B. the preparation of active component ruthenium salt is 1.013 * 10 in vacuum
-3～1.013 * 10
-4Under the Pa condition, the ruthenium powder is carried out chlorination reaction at 50～250 ℃, make ruthenic chloride;
C. ruthenic chloride salt is made the solution of 10～100g/l, the control temperature is in the time of 10～100 ℃, and the activated carbon of handling through reactivation with this solution impregnation under brute force stirs makes ruthenium load on the activity carbon carrier effectively;
D. with being selected from a kind of or any mixture more than two kinds in azanol, formaldehyde hydrazine hydrate and the hydrogen, under 0-100 ℃ of temperature, make the activation processing that catalyst carries out 180-360 minute to said process is made, filter, spend deionised water to Cl
-＜1 * 10
-6M is 120-220 ℃ in temperature at last, and vacuum is 1.013 * 10
-3～1.013 * 10
-4Dry under the Pa condition, under nitrogen protection, come out of the stove.
Noble metals hydrogenation catalyst of ruthenium/carbon loaded type of the present invention is compared with traditional Rayleigh Raney nickel, can make the harshness of the working condition of original sorbierite require to be alleviated, and reaction temperature can be reduced to 105 ℃, and reaction pressure can be reduced to 3MPa.Adopt noble metals hydrogenation catalyst of ruthenium/carbon loaded type of the present invention to produce every sorbierite, only spent catalyst 0.1kg can reduce cost effectively, enhances productivity.And the present invention/its stable preparation process of c loaded noble metal hydrogenization catalyst preparation method is reliable, be with glucose be raw material produce sorbierite the reaction of pure fluidisation attitude the time a kind of more satisfactory catalyst.
, be further described a kind of noble metals hydrogenation catalyst of ruthenium/carbon loaded type of the present invention and preparation method thereof below in conjunction with example.
A kind of noble metals hydrogenation catalyst of ruthenium/carbon loaded type comprises on activated carbon and the supported active carbon and the metal Ru of activated processing that wherein the content of ruthenium is: 4.8～5.3%, and Cl
-6＜1 * 10
-6M, Fe＜1 * 10
-4M, Pb＜1 * 10
-4M, Cu＜1 * 10
-4M, all the other are activated carbon and unavoidable impurities.
The specific area of catalyst activity carbon carrier is at 600～1300m/g, and pore volume is 0.2～2.2ml/g, particle size distribution: 100%＜210 μ m.
Preparation method of the present invention comprises following four steps.
1. the selection of carbon carrier and processing
The activated carbon that is used for carrier of the present invention needs foot state index request through selection:
| Index | Data |
| Absorption affinity, methylene blue (milligram/gram activated carbon) 〉=iodine sorption value moisture content (%) pH value＜molysite (%) granularity (%)＜200 μ m | ??????280 ??????75 ??????10-15 ??????3.0～7.0 ??????0.02 ??????1000 |
Above detection method is conventional method.
Through checking satisfactory activated carbon, must be through vacuum, high-temperature process, so that have intensity and activity, and remove thermal decomposition product and other harmful impurity of remained on surface.Vacuum during processing is 1.013 * 10
-3～1.013 * 10
-4Pa, temperature is under 500-1200 ℃, constant temperature 10-30 hour.Come out of the stove to room temperature in slow cooling under the above-mentioned vacuum condition.The specific area of treated activity carbon carrier is 600～1300m/g, and pore volume is 0.2～2.2ml/g.
2. active component-ruthenium compound is synthetic
" the metal Ru powder purity that preparation ruthenium chemical combination is used " 99.95%.Its chemical composition meets following table and requires:
| ?Ru，％ ???＞ | Impurity, % (≤) | |||||||
| ??Pt | ??Tr | ??Ag | ??P | ??Fe | ???Cu | ???Pb | ?????Al | |
| ?99.95 | ?0.003 | ?0.005 | ?0.005 | ?0.001 | ?0.002 | ??0.002 | ?0.0005 | ???0.0008 |
The ruthenium compound method for making is as follows:
Take by weighing the ruthenium powder and place reative cell, being evacuated to vacuum is 1.013
-3* 10～1.013 * 10
-4During Pa, feed chlorine flowrate and reach 50-200m/l, be warming up to 50-250 ℃, carry out chlorination reaction, make RuCl
3RuCl
4Mixture, with azanol reduction high price ruthenic chloride, obtain at a low price, the ruthenic chloride of Yi Rong.
3. the deposition of ruthenium salt on carrier
Preparation system concentration is the ruthenium salting liquid of 10-100g/l, comes the carrier activated carbon handled in the impregnation steps 1 with this.This process is equipped with powerful the stirring, and the control temperature during constant temperature method, is soaked the activated carbon of handling through reactivation clearly with this solution under brute force stirs in 10-100 ℃ of scope, ruthenium is loaded on the activity carbon carrier effectively.
4. the activation of ruthenium-containing catalyst
The purpose of this technology is that the noble metal active component is carried on the inside and outside surface of carrier with the even fine particle of polymolecularity.A kind of or any mixture more than two kinds with being selected from azanol, formaldehyde hydrazine hydrate and the hydrogen carries out activation processing to catalyst, and temperature is controlled at 0-100 ℃, and the processing time is 180-360 minute.Spend deionised water after leaching to Cl
-＜1 * 10
-6M is 120-220 ℃ in temperature at last, and vacuum is 1.013 * 10
-3～1.013 * 10
-4Under the Pa spare dry 48-70 hour, under nitrogen protection, reduce to room temperature and come out of the stove.
The invention will be further described below in conjunction with instantiation.
Embodiment 1
Selecting absorption affinity is 300, and iodine sorption value is 85, moisture content 10%, and pH value=3.5, molysite content is 0.01%, and granularity is that 40 μ m account for 50%, and all the other are the pure powdered activated carbon 50g of analysis of 65-210 μ m, are 1.013 * 10 in vacuum
-4In the vacuum drying oven of Pa, be warming up to 1100 ℃, be incubated after 10 hours, slow cooling to temperature is come out of the stove, and the activated carbon specific area of handling is 736m, and pore volume is 0.34ml/g.
Taking by weighing 3.0g metal Ru powder, is 1.013 * 10 in vacuum
-3Chlorination under the Pa.Chlorine flowrate is 60ml/h, and heating-up temperature is 100 ℃, after reaction is slowed down, stops heating, be cooled to room temperature after, with azanol ruthenium compound is reduced at a low price ruthenic chloride.
Compound concentration is the ruthenium salting liquid of 10g/l, under temperature is 10 ℃ and powerful the stirring, adds treated carrier carbon, and constant temperature method 3 hours leaves standstill after 48 hours with hydrazine and it carried out activation processing 4 ℃ the time, and the time is 120 minutes.Leach the catalyst that makes, wash to pH=6.35 Cl with a large amount of deionized waters
-Concentration＜1 * 10
-6M is 1.013 * 10 in 200 ℃ of temperature and vacuum then
-3Under the Pa, vacuum drying 68 hours.Dropping to room temperature in nitrogen protection at last comes out of the stove.
Example 2
Selecting absorption affinity is 285, and iodine sorption value is 79, moisture content 13%, and pH value=3.5, molysite content is 0.013%, and granularity is that 30-40 μ m accounts for 60%, and all the other are the pure powdered activated carbon 50g of analysis of 100-1800 μ m, are 1.013 * 10 in vacuum
-4In the vacuum drying oven of Pa, be warming up to 980 ℃, be incubated after 14 hours, slow cooling to temperature is come out of the stove, and the activated carbon specific area of handling is 798m/g, and pore volume is 0.42ml/g.
Taking by weighing 5.0g metal Ru powder, is 1.013 * 10 in vacuum
-3Chlorination under the Pa.Chlorine flowrate is 80ml/h, and heating-up temperature to 130 ℃ after reaction is slowed down, stops heating, be cooled to room temperature after, with azanol ruthenium compound is reduced into ruthenic chloride at a low price.
Compound concentration is the ruthenium salting liquid of 18g/l, under temperature is 20 ℃ and powerful the stirring, adds treated carrier carbon, and constant temperature method 2.5 hours leaves standstill after 60 hours with hydrazine and it carried out activation processing 4 ℃ the time, and the time is 180 minutes.Leach the catalyst that makes, with a large amount of rinsed with deionized water to pH=6.80, Cl
-Concentration＜1 * 10
-6M is 1.013 * 10 in 150 ℃ of temperature and vacuum then
-3Under the Pa, vacuum drying 60 hours.Dropping to room temperature in nitrogen protection at last comes out of the stove.
Example 3
Selecting absorption affinity is 300, and iodine sorption value is 85, moisture content 10%, and pH value=4.3, molysite content is 0.012%, and granularity is that 40 μ m account for 50%, and all the other are the pure powdered activated carbon 50g of analysis of 65-210 μ m, are 1.013 * 10 in vacuum
-4In the vacuum drying oven of Pa, be warming up to 1100 ℃, be incubated after 16 hours, slow cooling to temperature is come out of the stove, and the activated carbon specific area of handling is 746m/g, and pore volume is 0.38ml/g.
Taking by weighing 5.0g metal Ru powder, is 1.013 * 10 in vacuum
-3Chlorination under the Pa.Chlorine flowrate is 80ml/h, and heating-up temperature is 100 ℃, after reaction is slowed down, stops heating, be cooled to room temperature after, with azanol ruthenium compound is reduced at a low price ruthenic chloride.
Compound concentration is the ruthenium salting liquid of 10g/l, under temperature is 16 ℃ and powerful the stirring, adds treated carrier carbon, constant temperature method 3 hours, leave standstill after 48 hours with hydrazine 10 ℃ with pH=8.4 under, it is carried out activation processing, the time is 21 minutes.Leach the catalyst that makes, wash to PH=6.35 Cl with a large amount of deionized waters
-Concentration＜1 * 10
-6M is 1.013 * 10 in 200 ℃ of temperature and vacuum then
-6Under the Pa, vacuum drying 70 hours.Dropping to room temperature in nitrogen protection at last comes out of the stove.
Embodiment 4
Selecting absorption affinity is 280, and iodine sorption value is 75, moisture content 15%, and pH value=6.9, molysite content is 0.02%, granularity is the pure powdered activated carbon 50g of the analysis of 65-210 μ m, is 1.013 * 10 in vacuum
-4In the vacuum drying oven of Pa, be warming up to 800 ℃, be incubated after 30 hours, slow cooling to temperature is come out of the stove, and the activated carbon specific area of handling is 678m, and pore volume is 0.21ml/g.
Taking by weighing 3.0g metal Ru powder, is 1.013 * 10 in vacuum
-3Chlorination under the Pa.Chlorine flowrate is 120l/h, and heating-up temperature is 180 ℃, after reaction is slowed down, stops heating, be cooled to room temperature after, with azanol ruthenium compound is reduced at a low price ruthenic chloride.
Compound concentration is the ruthenium salting liquid of 10g/l, under temperature is 100 ℃ and powerful the stirring, adds treated carrier carbon, constant temperature method 3 hours, leave standstill after 48 hours with hydrazine 60 ℃ with pH=4.8 under it is carried out activation processing, the time is 210 minutes.Leach the catalyst that makes, wash to pH=6.35 Cl with a large amount of deionized waters
-Concentration＜1 * 10
-6M is 1.013 * 10 in 125 ℃ of temperature and vacuum then
-3Under the Pa, vacuum drying 60 hours.Dropping to room temperature in nitrogen protection at last comes out of the stove.
Embodiment 5
The performance qualified activity carbon carrier of selection through handling with method among the embodiment 1.Take by weighing 3.0g metal Ru powder,, produce ruthenic chloride with chlorination among the embodiment 1.With the ruthenic chloride that makes respectively compound concentration be the ruthenium salting liquid of 5g/l, 3g/l and 2g/l, the carrier carbon of dividing 3 adsorption treatment to cross under brute force stirs should be washed behind each dipping, drying, carries out next step absorption again.Be adsorbed onto drying is all undertaken by technology among the embodiment 1. at every turn.Activating finished product handles with embodiment 2.
Use noble metals hydrogenation catalyst of ruthenium/carbon loaded type of the present invention, the reaction temperature when producing sorbierite can be reduced to 105 ℃, and reaction pressure can be reduced to 3MPa.Adopt noble metals hydrogenation catalyst of ruthenium/carbon loaded type of the present invention to produce every sorbierite, only spent catalyst 0.1kg can reduce cost effectively, enhances productivity.And the present invention/its stable preparation process of c loaded noble metal hydrogenization catalyst preparation method is reliable, is with glucose be a kind of more satisfactory catalyst of raw material when producing the fluidized-bed reaction of sorbierite.
Claims (3)
1. noble metals hydrogenation catalyst of ruthenium/carbon loaded type, it is characterized in that: catalyst comprises by activated carbon and is carried on the activated carbon and the metal Ru of activated processing is formed, the content of ruthenium is: 4.8～5.3%, and all the other are activated carbon and unavoidable impurities, wherein
Cl
-＜1×10
-6M，
Fe＜1×10
-4M，
Pb＜1×10
-4M，
Cu＜1×10
-4M。
2. a kind of noble metals hydrogenation catalyst of ruthenium/carbon loaded type according to claim 1, the specific area of its catalyst activity carbon carrier are 600～1300m/g, and pore volume is 0.2～2.2ml/g, particle size distribution: 100%＜210 μ m.
3. the preparation method of a noble metals hydrogenation catalyst of ruthenium/carbon loaded type comprises the selection of carbon carrier and reactivation processing, the preparation of active constituent ruthenium, the deposition of active constituent ruthenium salt on carbon carrier, the activation processing of catalyst, it is characterized in that:
A. after selecting satisfactory activated carbon, be 1.013 * 10 in vacuum
-3～1.013 * 10
-4Pa, being warming up to temperature is under 500-1200 ℃, further activates and intensive treatment under constant temperature 10-30 hour condition;
B. the preparation of active component ruthenium salt is 1.013 * 10 in vacuum
-3～1.013 * 10
-4Under the Pa condition, the ruthenium powder is carried out chlorination reaction at 50-250 ℃, make ruthenic chloride;
C. ruthenic chloride salt is made the solution of 10-100g/l, the control temperature is in the time of 10-100 ℃, and the activated carbon of handling through reactivation with this solution impregnation under brute force stirs makes ruthenium load on the activity carbon carrier effectively;
D. with being selected from a kind of or any mixture more than two kinds in azanol, formaldehyde hydrazine hydrate and the hydrogen, under 0-100 ℃ of temperature, make the activation processing that catalyst carries out 180-360 minute to said process is made, filter and spend deionised water to Cl
-＜1 * 10
-6M is 120-220 ℃ in temperature at last, and vacuum is 1.013 * 10
-3～1.013 * 10
-4Dry under the Pa condition, under nitrogen protection, come out of the stove.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97103653 CN1048193C (en) | 1997-03-27 | 1997-03-27 | Noble metals hydrogenation catalyst of ruthenium/carbon loaded type, and method for preparing same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97103653 CN1048193C (en) | 1997-03-27 | 1997-03-27 | Noble metals hydrogenation catalyst of ruthenium/carbon loaded type, and method for preparing same |
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| Publication Number | Publication Date |
|---|---|
| CN1161252A true CN1161252A (en) | 1997-10-08 |
| CN1048193C CN1048193C (en) | 2000-01-12 |
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304112C (en) * | 2001-12-07 | 2007-03-14 | 巴斯福股份公司 | Preparation of ruthenium/iron catalyst loaded onto carbon |
| CN101259411B (en) * | 2008-04-16 | 2010-06-09 | 厦门大学 | Catalyst for preparing diesel fraction hydrocarbons and preparation method thereof |
| CN101966457A (en) * | 2010-09-25 | 2011-02-09 | 郴州高鑫铂业有限公司 | Method for preparing high-activity carbonyl hydrogenation ruthenium-carbon catalyst |
| CN107096528A (en) * | 2017-03-30 | 2017-08-29 | 华南理工大学 | A kind of bagasse carbonization load biomass-based catalyst of ruthenium and preparation method and application |
| CN107362797A (en) * | 2017-07-24 | 2017-11-21 | 郴州高鑫铂业有限公司 | Nano ruthenium carbon catalyst and preparation method thereof and its application in 4,4 ' diamino-dicyclohexyl methanes are synthesized |
| CN109364984A (en) * | 2018-12-06 | 2019-02-22 | 浙江工业大学 | A kind of ZSM-5 molecular sieve supported ruthenium catalyst and its preparation and application |
| WO2020114287A1 (en) * | 2018-12-06 | 2020-06-11 | 浙江工业大学 | Ruthenium-nickel/activated carbon co-supported catalyst, preparation thereof and use thereof |
| CN111545196A (en) * | 2020-05-20 | 2020-08-18 | 长春黄金研究院烟台贵金属材料研究所有限公司 | Preparation method of ruthenium-carbon catalyst for selective hydrogenation |
-
1997
- 1997-03-27 CN CN 97103653 patent/CN1048193C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304112C (en) * | 2001-12-07 | 2007-03-14 | 巴斯福股份公司 | Preparation of ruthenium/iron catalyst loaded onto carbon |
| CN101259411B (en) * | 2008-04-16 | 2010-06-09 | 厦门大学 | Catalyst for preparing diesel fraction hydrocarbons and preparation method thereof |
| CN101966457A (en) * | 2010-09-25 | 2011-02-09 | 郴州高鑫铂业有限公司 | Method for preparing high-activity carbonyl hydrogenation ruthenium-carbon catalyst |
| CN101966457B (en) * | 2010-09-25 | 2012-07-25 | 郴州高鑫铂业有限公司 | Method for preparing high-activity carbonyl hydrogenation ruthenium-carbon catalyst |
| CN107096528A (en) * | 2017-03-30 | 2017-08-29 | 华南理工大学 | A kind of bagasse carbonization load biomass-based catalyst of ruthenium and preparation method and application |
| CN107362797A (en) * | 2017-07-24 | 2017-11-21 | 郴州高鑫铂业有限公司 | Nano ruthenium carbon catalyst and preparation method thereof and its application in 4,4 ' diamino-dicyclohexyl methanes are synthesized |
| CN109364984A (en) * | 2018-12-06 | 2019-02-22 | 浙江工业大学 | A kind of ZSM-5 molecular sieve supported ruthenium catalyst and its preparation and application |
| WO2020114287A1 (en) * | 2018-12-06 | 2020-06-11 | 浙江工业大学 | Ruthenium-nickel/activated carbon co-supported catalyst, preparation thereof and use thereof |
| CN111545196A (en) * | 2020-05-20 | 2020-08-18 | 长春黄金研究院烟台贵金属材料研究所有限公司 | Preparation method of ruthenium-carbon catalyst for selective hydrogenation |
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| Publication number | Publication date |
|---|---|
| CN1048193C (en) | 2000-01-12 |
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Assignee: Xi'An Catalyst Chemical Co., Ltd. Assignor: Xibei Non-ferrous Metals Research Inst. Contract fulfillment period: 2006.6.20 to 2017.3.26 contract change Contract record no.: 2009610000025 Denomination of invention: Noble metals hydrogenation catalyst of ruthenium/carbon loaded type, and method for preparing same Granted publication date: 19991113 License type: General permission Record date: 20091123 |
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