CN102824915A - Catalyst for preparing lower-carbon glycols through hydrogenolysis of C5 and C6 sugar alcohol mixture and preparation method of catalyst - Google Patents
Catalyst for preparing lower-carbon glycols through hydrogenolysis of C5 and C6 sugar alcohol mixture and preparation method of catalyst Download PDFInfo
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- CN102824915A CN102824915A CN2012102579965A CN201210257996A CN102824915A CN 102824915 A CN102824915 A CN 102824915A CN 2012102579965 A CN2012102579965 A CN 2012102579965A CN 201210257996 A CN201210257996 A CN 201210257996A CN 102824915 A CN102824915 A CN 102824915A
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Abstract
The invention provides a catalyst for preparing lower-carbon glycols through hydrogenolysis of a C5 and C6 sugar alcohol mixture, a preparation method, and an application of the catalyst. The catalyst comprises nickel, tin and active carbon based on the mass ratio of (5 to 50): (5 to 50): 100. Compared with the prior art, the catalyst has the advantages that the C5 and C6 sugar alcohol mixture is used as the raw material; the nickel and the tin are served as the active components of the catalyst; and the active carbon is served as a carrier; the catalyst prepared by the preparation method provided by the invention has high selectivity. With the adoption of the catalyst and the preparation method of the catalyst, the raw materials are not needed to be separated and fined, so the cost is low; common metals are served as the active components, so that the cost of the catalyst is lower; the product lower-carbon glycols have good selectivity, so the economical efficiency is high.
Description
Technical field
The present invention relates to catalyst, preparation method and application in the biochemical field, specifically refer to a kind of catalyst, preparation method and application of nickel tin hydrogenolysis sugar alcohol mixtures.
Technical background
Whole world sugar alcohol application is distributed as food processing industry and accounts for 42%, and cosmetics and personal hygiene article are about 22%, and the raw material of chemical products is about 21%, pharmaceutical sector about 15%.The low-carbon (LC) dihydroxylic alcohols mainly refers to ethylene glycol, propane diols, butanediol etc.Ethylene glycol is used for synthetic resin, fiber, plasticizer, cosmetics and explosive, and as solvent, the antifreeze of preparation engine etc.Propane diols is the important source material of unsaturated polyester (UP), epoxy resin, polyurethane resin, and its aqueous solution still is effective antifreeze.
The technology that with the oil is raw material production low-carbon (LC) dihydroxylic alcohols is ripe, but energy crisis is serious day by day, and contradiction between oil supply and demand is outstanding.Prepare the approach that the low-carbon (LC) dihydroxylic alcohols has been proved to be practical a, sustainable development by living resources.The contradiction of great demand and resource scarcity shows that exploitation is produced the low-carbon (LC) dihydroxylic alcohols with living resources has very big development space.
CN200810017788.1 has announced " a kind of method of being produced low carbon chemical alcohol by the C6 sugar alcohol ".It is characterized in that " in the presence of alkali condition and nickel/palladium catalyst for cracking; in the proportioning of aqueous phase C6 sugar alcohol in the aqueous solution is 30-60% (w/v) "; The weight that described C6 sugar alcohol water cracking generates sugar alcohol mixtures consists of: ethylene glycol 20-50%; Propane diols 35-65%, glycerine 10-20%, various butanediol isomers 8-20%.
CN1683293A has announced " a kind of method of being produced dihydroxylic alcohols and sugar alcohol by cracking sorbierite ".This method comprises " in the presence of NaOH and nickel/ruthenium catalyst for cracking, in the mixture of HTHP with sorbierite hydrocracking generation C2-4 dihydroxylic alcohols and sugar alcohol, behind separation and purification, obtaining single product respectively ".It is characterized in that described sorbierite carries out hydrocracking and generates C2-4 dihydroxylic alcohols and other alcohol mixture, weight consists of: ethylene glycol 15-30%, propane diols 30-60%, glycerine 15-30%, various butanediol isomers 5-12%.
Above-mentioned two kinds of nickel/palladium and nickel/ruthenium catalysts that adopted by the method for sorbierite production low carbon chemical alcohol contain palladium and ruthenium noble metal respectively, and the catalyst cost is higher; Raw material C6 sugar alcohol or sorbierite need pass through to separate and make with extra care and just can obtain, and production procedure is complicated, and equipment investment is big, and cost is higher.Therefore, " Catalysts and its preparation method of a kind of C5, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols " of the present invention is novel, and existing document does not have careful report so comprehensively as yet.
Summary of the invention
Content of the present invention provides the Catalysts and its preparation method of a kind of C5, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols, reaches active preferably in conjunction with proper technical conditions, thereby C5, C6 sugar alcohol mixtures are converted into the low-carbon (LC) dihydroxylic alcohols selectively.
Method for preparing catalyst of the present invention is that a certain amount of nickel compound, tin compound is water-soluble, adds in the carrier, process catalyst precursor after, in the reduction of High Purity Hydrogen atmosphere, air passivation is used in the cooling back, obtains black powder shape solid catalyst.
Catalyst activity charcoal carrier of the present invention can be wood activated charcoal, active carbon from coal or cocoanut active charcoal, preferred cocoanut active charcoal.
Described method for preparing catalyst comprises that the method with nickel compound and tin compound introducing absorbent charcoal carrier can be any technique known; Like method commonly used with solution nickeliferous, the tin component; Add precipitating reagent, prepare catalyst sample with the precipitation method with carrier.
Catalyst reduction process of the present invention is: after installing catalyst, introduce N2 and H2 mist, nitrogen and hydrogen preferred proportion are 0.2-0.5, are warming up to 200-250 ℃, stablize 0.5～2.5, preferred 1-2 hour stabilization time; Be warmed up to 350-450 ℃ afterwards, adopt 100% pure hydrogen reduction, the recovery time is 1～3 hour.Reduce to room temperature, use nitrogen replacement, introduce air passivation, obtain black powder shape solid catalyst.
After the described catalyst reduction of the inventive method, catalyst selectivity has obvious lifting.
Described nickel compound containing is selected from one or more in the nickeliferous soluble compound, like in the soluble complexes of nickel nitrate, nickel chloride and nickel one or more, and preferred nickel nitrate, nickel chloride wherein.
Described sn-containing compound is selected from one or more in the soluble compound of stanniferous, like in stannous chloride, stannic chloride, the stannate one or more, and preferred stannous chloride, stannic chloride wherein.
Catalyst of the present invention is specially adapted to C5, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols.
Described C5, C6 sugar alcohol mixtures are the aqueous solution of 10-95% weight, and wherein the C5 sugar alcohol is xylitol, arabitol etc., and content is 5～55 weight %; The C6 sugar alcohol is sorbierite, sweet mellow wine etc., and content is 5～45 weight %.When the catalyst that uses the inventive method to prepare carried out hydrogenolysis system low-carbon (LC) dihydroxylic alcohols, C5, C6 sugar alcohol mixtures need not purified, and can in mixture, carry out cracking reaction.
In tank reactor, catalyst performance is estimated demonstration, this catalyst can be selectively with C5, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols under certain hydrocracking condition.
Described hydrocracking condition comprises that reaction for still reaction, is reflected at and carries out under the alkali condition, and the pH value is preferably 9.5-10.5 in the 9-11 scope; Reaction temperature is 230-255 ℃, is preferably 230-240 ℃; Reaction pressure is 6-12MPa, is preferably 8-11Mpa; Reaction time is 1.5～5 hours, is preferably 2～4 hours; The catalyst addition is the 2-10% weight of amount of sugar alcohol, is preferably 5-8% weight.
Described weight with C5, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols consists of: ethylene glycol 20-50%; Propane diols 30-60%; Butanediol 2-10%; Residue is the less fusel 0-15% of other content.
Prepare catalyst according to the method described in the present invention and carry out C5, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols; Because catalyst has good selectivity; The ethylene glycol, propane diols and the butanediol that contain high level, its added value of product is far above the product that makes with other patent of invention methods.
The specific embodiment
Following embodiment will be described further the present invention.
Agents useful for same among the embodiment except that specifying, is chemically pure reagent.
Embodiment 1
With 30g NiCl
26H
2O and 9.6g SnCl
22H
2O is dissolved in the 300mL distilled water, stirs down to add 50 g coconut shell flour shaped activated carbons (200 orders, 100 mL) dipping 24 h under the room temperature.Under stirring condition, the 16%NaOH aqueous solution is slowly joined in the above-mentioned mixed liquor, the adjusting pH value is 6-7, is heated with stirring to boiling, is cooled to room temperature then, filters, and washing in 120 ℃ of dryings, obtains catalyst precursor with solid to there not being chlorion.Catalyst precursor heats up in nitrogen and hydrogen gas mixture, under 200 ℃, stablizes 2 hours, continues to be warming up to 400 ℃, adopts 100% pure hydrogen reduction, and the recovery time is 2 hours.Reduce to room temperature, use nitrogen replacement, introduce air passivation, obtain black powder shape solid catalyst CAT1.
Hydrogenolysis is a still reaction; In agitated reactor, add mass percent and be 45% C5, the C6 sugar alcohol mixtures aqueous solution; The catalyst addition is 5% (mass percent) of amount of sugar alcohol, and using 45% sodium hydrate regulator solution pH value is 10, and reaction temperature is 250 ℃; The maintenance Hydrogen Vapor Pressure is 9MPa, and the reaction time is 180 minutes.Reaction finishes after the liquid-phase chromatographic analysis result is following:
The comparative example 1
With 30g NiCl
26H
2O and 5.3g RuCl
23H
2O is dissolved in the 300 mL distilled water, stirs down to add 50 g coconut shell flour shaped activated carbons (200 orders, 100 mL) dipping 24 h under the room temperature.Under stirring condition, the 16%NaOH aqueous solution is slowly joined in the above-mentioned mixed liquor, the adjusting pH value is 6-7, is heated with stirring to boiling, is cooled to room temperature then, filters, and washing in 120 ℃ of dryings, obtains catalyst precursor with solid to there not being chlorion.Catalyst precursor heats up in nitrogen and hydrogen gas mixture, under 200 ℃, stablizes 2 hours, continues to be warming up to 400 ℃, adopts 100% pure hydrogen reduction, and the recovery time is 2 hours.Reduce to room temperature, use nitrogen replacement, introduce air passivation, obtain black powder shape solid catalyst CAT2.
Hydrogenolysis is a still reaction; In agitated reactor, add mass percent and be 45% C5, the C6 sugar alcohol mixtures aqueous solution; The catalyst addition is 5% (mass percent) of amount of sugar alcohol, and using 45% sodium hydrate regulator solution pH value is 10, and reaction temperature is 250 ℃; Keeping Hydrogen Vapor Pressure is 9 MPa, and the reaction time is 180 minutes.Reaction finishes after the liquid-phase chromatographic analysis result is following:
Embodiment 2
With 60g NiCl
26H
2O and 19.22g SnCl
22H
2O is dissolved in the 450 mL distilled water, stirs down to add 50 g wood powder shaped activated carbons (200 orders, 100 mL) dipping 12 h under the room temperature.Under stirring condition, the 16%NaOH aqueous solution is slowly joined in the above-mentioned mixed liquor, the adjusting pH value is 6-7, is heated with stirring to boiling, is cooled to room temperature then, filters, and washing in 120 ℃ of dryings, obtains catalyst precursor with solid to there not being chlorion.Catalyst precursor heats up in nitrogen and hydrogen gas mixture, under 250 ℃, stablizes 2 hours, continues to be warming up to 450 ℃, adopts 100% pure hydrogen reduction, and the recovery time is 3 hours.Reduce to room temperature, use nitrogen replacement, introduce air passivation, obtain black powder shape solid catalyst CAT3.
Hydrogenolysis is a still reaction; In agitated reactor, add mass percent and be 45% C5, the C6 sugar alcohol mixtures aqueous solution; The catalyst addition is 5% (mass percent) of amount of sugar alcohol, and using 45% sodium hydrate regulator solution pH value is 10, and reaction temperature is 250 ℃; Keeping Hydrogen Vapor Pressure is 10 MPa, and the reaction time is 4 hours.Reaction finishes after the liquid-phase chromatographic analysis result is following:
Embodiment 3
With 293.0g Ni (NO
3)
26H
2O and 76.9g SnCl
22H
2O is dissolved in the 2000 mL distilled water, and (200 orders 450mL), flood 12 h under the room temperature to add 200 g ature of coal powdered activated carbons under stirring.Under stirring condition, the 16%NaOH aqueous solution is slowly joined in the above-mentioned mixed liquor, the adjusting pH value is 6-7, is heated with stirring to boiling; Be cooled to room temperature then, filter, washing is to not having chlorion and nitrate ion; Solid in 120 ℃ of dryings, is obtained catalyst precursor.Catalyst precursor heats up in nitrogen and hydrogen gas mixture, under 250 ℃, stablizes 2 hours, continues to be warming up to 450 ℃, adopts 100% pure hydrogen reduction, and the recovery time is 3 hours.Reduce to room temperature, use nitrogen replacement, introduce air passivation, obtain black powder shape solid catalyst CAT4.
Hydrogenolysis is a still reaction; In agitated reactor, add mass percent and be 65% C5, the C6 sugar alcohol mixtures aqueous solution; The catalyst addition is 8% (mass percent) of amount of sugar alcohol, and using 45% sodium hydrate regulator solution pH value is 10, and reaction temperature is 250 ℃; Keeping Hydrogen Vapor Pressure is 11 MPa, and the reaction time is 2 hours.Reaction finishes after the liquid-phase chromatographic analysis result is following:
Embodiment 4
With 300g Ni (NO
3)
26H
2O and 90g Sn (NO
3)
2Be dissolved in the 2000 mL distilled water, (200 orders 400mL), flood 24 h under the room temperature to add 200 g coconut shell flour shaped activated carbons under stirring.Under stirring condition, the 16%NaOH aqueous solution is slowly joined in the above-mentioned mixed liquor, the adjusting pH value is 6-7, is heated with stirring to boiling, is cooled to room temperature then, filters, and washing in 120 ℃ of dryings, obtains catalyst precursor with solid to there not being nitrate ion.Catalyst precursor heats up in nitrogen and hydrogen gas mixture, under 200 ℃, stablizes 2 hours, continues to be warming up to 400 ℃, adopts 100% pure hydrogen reduction, and the recovery time is 2 hours.Reduce to room temperature, use nitrogen replacement, introduce air passivation, obtain black powder shape solid catalyst CAT5.
Hydrogenolysis is a still reaction; In agitated reactor, add mass percent and be 55% C5, the C6 sugar alcohol mixtures aqueous solution; The catalyst addition is 10% (mass percent) of amount of sugar alcohol, and using 45% sodium hydrate regulator solution pH value is 10, and reaction temperature is 250 ℃; Keeping Hydrogen Vapor Pressure is 10 MPa, and the reaction time is 2 hours.Reaction finishes after the liquid-phase chromatographic analysis result is following:
Claims (7)
1. the catalyst of a C5, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols is characterized in that being made up of the nickel of absorbent charcoal carrier and 5-50 weight % and the tin of 5-50% weight.
2. the catalyst of a kind of C5 as claimed in claim 1, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols; It is characterized in that described C5, C6 sugar alcohol mixtures are the aqueous solution of 10～95% weight; Wherein the C5 sugar alcohol is xylitol, arabitol etc., and content is 5～55 weight %; The C6 sugar alcohol is sorbierite, sweet mellow wine etc., and content is 5～45 weight %.
3. the catalyst of a kind of C5 as claimed in claim 1, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols is characterized in that described low-carbon (LC) dihydroxylic alcohols is ethylene glycol, propane diols and butanediol.
4. the catalyst of a kind of C5 as claimed in claim 1, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols is characterized in that said absorbent charcoal carrier is wood activated charcoal, coal mass active carbon or cocoanut active charcoal, preferred cocoanut active charcoal.
5. the catalyst of a kind of C5 as claimed in claim 1, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols is characterized in that said nickel and tin derive from respective metal salt, and said slaine is chlorate or nitrate.
6. a kind of C5 as claimed in claim 1, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols Preparation of catalysts method is characterized in that may further comprise the steps:
1) take by weighing quantitative nickel salts, pink salt is water-soluble, is mixed with 5%～20% aqueous solution, add then in the quantitative absorbent charcoal carrier; Liquid-solid volume ratio is 1: 1～6: 1; Flooded under the room temperature 12～24 hours, and under agitation slowly joined in the above-mentioned mixed liquor with 10%～20% sodium hydrate aqueous solution, regulating the pH value is 6～7; Be heated to boiling under stirring, be cooled to room temperature then;
2) filter, washing in 120 ℃ of dryings, obtains catalyst precursor with solid to not having chlorion or nitrate ion;
3) catalyst precursor heats up in nitrogen and hydrogen gas mixture, under 200～250 ℃, stablizes 0.5～2.5 hour, continues to be warming up to 350～450 ℃, adopts 100% pure hydrogen reduction, and the recovery time is 1～3 hour.Reduce to room temperature, use nitrogen replacement, introduce air passivation, obtain black powder shape solid catalyst.
7. the catalyst of a kind of C5 as claimed in claim 1, C6 sugar alcohol mixtures hydrogenolysis system low-carbon (LC) dihydroxylic alcohols; It is characterized in that described hydrogenolysis is a still reaction, be reflected under the alkali condition to carry out that the pH value is in 9～11 scopes; Reaction temperature is 230～255 ℃; Reaction pressure is 6～12MPa, and the reaction time is 1.5～5 hours, and the catalyst addition is 2～10% weight of amount of sugar alcohol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111375421A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon dihydric alcohol by hydrogenolysis of saccharides and preparation method thereof |
| CN112552528A (en) * | 2020-11-19 | 2021-03-26 | 万华化学集团股份有限公司 | Method for removing solvent in high-temperature-resistant polymer solution |
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| CN102091624A (en) * | 2010-12-01 | 2011-06-15 | 厦门大学 | Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof |
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2012
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Patent Citations (3)
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| JPS5236609A (en) * | 1975-09-16 | 1977-03-22 | Takeda Chem Ind Ltd | Process for preparation of alcohol and carbon monoxide |
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Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111375421A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon dihydric alcohol by hydrogenolysis of saccharides and preparation method thereof |
| CN112552528A (en) * | 2020-11-19 | 2021-03-26 | 万华化学集团股份有限公司 | Method for removing solvent in high-temperature-resistant polymer solution |
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