CN102824915B - A kind of catalyst of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol and preparation method thereof - Google Patents
A kind of catalyst of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol and preparation method thereof Download PDFInfo
- Publication number
- CN102824915B CN102824915B CN201210257996.5A CN201210257996A CN102824915B CN 102824915 B CN102824915 B CN 102824915B CN 201210257996 A CN201210257996 A CN 201210257996A CN 102824915 B CN102824915 B CN 102824915B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carbon
- low
- sugar alcohol
- hydrogenolysis
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of catalyst of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol, preparation method and applications.The composition of catalyst is nickel, tin and activated carbon, and each component mass ratio is nickel: tin: activated carbon=(5 50): (5 50): 100 in catalyst.Compared with prior art, the advantage of the invention is that raw material uses C5, C6 sugar alcohol mixtures；Using nickel, tin as catalyst activity component, carrier is made with activated carbon；The catalyst obtained with the preparation method of the present invention, product selectivity is high.Therefore, raw material of the present invention does not need to separate and refine, with low cost；Make active constituent using common metal, catalyst cost is relatively low；Product low-carbon dihydric alcohol is selectively good, more economy.
Description
Technical field
The present invention relates to the catalyst in biochemical field, preparation method and application, a kind of nickel tin hydrogenolysis sugar is referred specifically to
The catalyst of alcohol mixture, preparation method and application.
Technical background
Global sugar alcohol application field is distributed as food processing industry and accounts for 42%, cosmetics and personal hygiene article about 22%,
The raw material of chemical products about 21%, pharmaceutical sector about 15%.Low-carbon dihydric alcohol refers mainly to ethylene glycol, propane diols, butanediol etc..Second two
Alcohol is used for synthetic resin, fiber, plasticizer, cosmetics and explosive, and as solvent, prepares antifreeze of engine etc..The third two
Alcohol is the important source material of unsaturated polyester (UP), epoxy resin, polyurethane resin, its aqueous solution or effective antifreeze.
The technology that low-carbon dihydric alcohol is produced by raw material of oil is ripe, but energy crisis is increasingly serious, oil supply and demand
It is particularly thorny.Low-carbon dihydric alcohol is prepared by living resources and has proved to be practical, sustainable development a approach.It is huge
The big market demand and the contradiction of resource scarcity show that develop has very big development empty with living resources production low-carbon dihydric alcohol
Between.
CN200810017788.1 is disclosed " a kind of method by C6 production of sugar polyol low carbon chemical alcohol ".It is characterized in that
" in the presence of alkalescence condition and nickel/palladium catalyst for cracking, the proportioning of C6 sugar alcohols in aqueous is 30-60% (w/ in aqueous phase
V) ", described C6 sugar alcohol aqueous phases be cracked to form sugar alcohol mixtures weight composition be：Ethylene glycol 20-50%, propane diols 35-
65%, glycerine 10-20%, various butanediol isomers 8-20%.
CN1683293A is disclosed " a kind of method that dihydric alcohol and sugar alcohol are produced by cracking sorbierite ".This method includes
" in the presence of sodium hydroxide and nickel/ruthenium catalyst for cracking, in HTHP by sorbierite hydrocracking generate C2-4 dihydric alcohols and
The mixture of sugar alcohol, respectively obtains single product after separation and purification ".It is characterized in that described sorbierite carries out hydrocracking
C2-4 dihydric alcohols and other alcohol mixtures are generated, weight composition is：Ethylene glycol 15-30%, propane diols 30-60%, glycerine 15-
30%, various butanediol isomers 5-12%.
Nickel/palladium and nickel/ruthenium catalyst that above two is used by the method for sorb alcohol production low carbon chemical alcohol, contain respectively
Palladium and ruthenium noble metal, catalyst cost are higher；Raw material C6 sugar alcohols or sorbierite need to can just be obtained by separating and refining, production stream
Journey is complicated, and equipment investment is big, and cost is higher.Therefore, " a kind of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon two of the present invention
Catalyst of first alcohol and preparation method thereof " is novel, and existing literature not yet has so comprehensive careful report.
The content of the invention
Present disclosure is to provide catalyst and its preparation of a kind of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol
Method, preferable activity is reached with reference to appropriate process conditions, so as to C5, C6 sugar alcohol mixtures are selectively converted into low
Carbon dihydric alcohol.
The method for preparing catalyst of the present invention is that a certain amount of nickel compound, tin compound are dissolved in into water, is added in carrier,
It is made after catalyst precursor, in the reduction of High Purity Hydrogen atmosphere, air passivation is used after cooling, black powder solid catalysis is obtained
Agent.
Catalyst activity high-area carbon of the present invention can be wood activated charcoal, active carbon from coal or cocoanut active charcoal,
It is preferred that cocoanut active charcoal.
Described method for preparing catalyst includes can be with by the method that nickel compound and tin compound introduce absorbent charcoal carrier
It is technology known to any one, such as solution of the conventional nickeliferous tin component of method, addition precipitating reagent, with carrier to precipitate
Method prepares catalyst sample.
Catalyst reduction process of the present invention is：Install after catalyst, introduce N2 and H2 mixed gas, nitrogen and hydrogen
Gas is preferably in a proportion of 0.2-0.5, is warming up to 200-250 DEG C, stablizes 0.5~2.5, preferably stabilization time 1-2 hours；Heat up afterwards
To 350-450 DEG C, using 100% pure hydrogen reduction, the recovery time is 1~3 hour.Room temperature is down to, with nitrogen displacement, air is introduced
Passivation, obtains black powder solid catalyst.
After the catalyst reduction described in the inventive method, catalyst choice is obviously improved.
One or more of the described nickel compound containing in nickeliferous soluble compound, such as nickel nitrate, nickel chloride
With the one or more in the soluble complexes of nickel, nickel nitrate, nickel chloride preferably wherein.
One or more of the described sn-containing compound in stanniferous soluble compound, such as stannous chloride, chlorination
One or more in tin, stannate, stannous chloride, stannic chloride preferably wherein.
Catalyst of the present invention is particularly suitable for use in C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol.
Described C5, C6 sugar alcohol mixtures are the aqueous solution of 10-95% weight, and wherein C5 sugar alcohols are xylitol, arabitol
It is 5~55 weight % Deng, content；C6 sugar alcohols are sorbierite, mannitol etc., and content is 5~45 weight %.Use the inventive method
When the catalyst prepared carries out hydrogenolysis low-carbon dihydric alcohol, C5, C6 sugar alcohol mixtures are not required to purification, can enter in the mixture
Row cracking reaction.
Evaluation is carried out to catalyst performance in tank reactor and shows that the catalyst is in certain hydrocracking conditions
Under, can be selectively by C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol.
It is still reaction that described hydrocracking conditions, which include reaction, and reaction is carried out in the basic conditions, and pH value is in 9-11
In the range of, preferably 9.5-10.5；Reaction temperature is 230-255 DEG C, preferably 230-240 DEG C；Reaction pressure is 6-12MPa,
Preferably 8-11Mpa；Reaction time is 1.5~5 hours, preferably 2~4 hours；Catalyst charge is the 2- of amount of sugar alcohol
10% weight, preferably 5-8% weight.
The described weight by C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol, which is constituted, is：Ethylene glycol 20-50%；Third
Glycol 30-60%；Butanediol 2-10%；Remaining as the less fusel 0-15% of other contents.
Catalyst is prepared according to the method described in the present invention carries out C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol,
Because catalyst has good selectivity, ethylene glycol, propane diols and butanediol containing high level, its added value of product are remote
Higher than with product made from other patent of invention methods.
Embodiment
The following examples illustrate the present invention further.
Agents useful for same in embodiment, is chemically pure reagent unless otherwise indicated.
Embodiment 1
By 30g NiCl2·6H2O and 9.6g SnCl2·2H2O is dissolved in 300mL distilled water, and stirring is lower to add 50 g coconut palms
Shell powdered activated carbon (200 mesh, 100 mL), impregnates 24 h at room temperature.The 16%NaOH aqueous solution is slowly added under agitation
Enter into above-mentioned mixed liquor, regulation pH value is 6-7, is heated with stirring to boiling, is subsequently cooled to room temperature, filter, washing is to without chlorine
Ion, by solid in 120 DEG C of dryings, obtains catalyst precursor.Catalyst precursor rises in nitrogen and hydrogen gas mixture
Temperature, in stablizing at 200 DEG C 2 hours, is continuously heating to 400 DEG C, using 100% pure hydrogen reduction, and the recovery time is 2 hours.It is down to
Room temperature, with nitrogen displacement, introduces air passivation, obtains black powder solid catalyst CAT1.
Hydrogenolysis is still reaction, and C5, C6 sugar alcohol mixtures water that mass percent is 45% are added in a kettle.
Solution, catalyst charge is 5% (mass percent) of amount of sugar alcohol, is 10 with 45% sodium hydrate regulator solution pH value, instead
It is 250 DEG C to answer temperature, and holding Hydrogen Vapor Pressure is 9MPa, and the reaction time is 180 minutes.React after terminating through liquid-phase chromatographic analysis knot
Fruit is as follows：
Comparative example 1
By 30g NiCl2·6H2O and 5.3g RuCl2·3H2O is dissolved in 300 mL distilled water, and stirring is lower to add 50 g coconut palms
Shell powdered activated carbon (200 mesh, 100 mL), impregnates 24 h at room temperature.The 16%NaOH aqueous solution is slowly added under agitation
Enter into above-mentioned mixed liquor, regulation pH value is 6-7, is heated with stirring to boiling, is subsequently cooled to room temperature, filter, washing is to without chlorine
Ion, by solid in 120 DEG C of dryings, obtains catalyst precursor.Catalyst precursor rises in nitrogen and hydrogen gas mixture
Temperature, in stablizing at 200 DEG C 2 hours, is continuously heating to 400 DEG C, using 100% pure hydrogen reduction, and the recovery time is 2 hours.It is down to
Room temperature, with nitrogen displacement, introduces air passivation, obtains black powder solid catalyst CAT2.
Hydrogenolysis is still reaction, and C5, C6 sugar alcohol mixtures water that mass percent is 45% are added in a kettle.
Solution, catalyst charge is 5% (mass percent) of amount of sugar alcohol, is 10 with 45% sodium hydrate regulator solution pH value, instead
It is 250 DEG C to answer temperature, and holding Hydrogen Vapor Pressure is 9 MPa, and the reaction time is 180 minutes.React after terminating through liquid-phase chromatographic analysis
As a result it is as follows：
Embodiment 2
By 60g NiCl2·6H2O and 19.22g SnCl2·2H2O is dissolved in 450 mL distilled water, and stirring is lower to add 50 g
Wooden powdered activated carbon (200 mesh, 100 mL), impregnates 12 h at room temperature.It is under agitation that the 16%NaOH aqueous solution is slow
It is added in above-mentioned mixed liquor, regulation pH value is 6-7, is heated with stirring to boiling, is subsequently cooled to room temperature, filters, washing to nothing
Chlorion, by solid in 120 DEG C of dryings, obtains catalyst precursor.Catalyst precursor is in nitrogen and hydrogen gas mixture
Heating, in stablizing at 250 DEG C 2 hours, is continuously heating to 450 DEG C, using 100% pure hydrogen reduction, and the recovery time is 3 hours.Drop
To room temperature, with nitrogen displacement, air passivation is introduced, black powder solid catalyst CAT3 is obtained.
Hydrogenolysis is still reaction, and C5, C6 sugar alcohol mixtures water that mass percent is 45% are added in a kettle.
Solution, catalyst charge is 5% (mass percent) of amount of sugar alcohol, is 10 with 45% sodium hydrate regulator solution pH value, instead
It is 250 DEG C to answer temperature, and holding Hydrogen Vapor Pressure is 10 MPa, and the reaction time is 4 hours.React after terminating through liquid-phase chromatographic analysis knot
Fruit is as follows：
Embodiment 3
By 293.0g Ni (NO3)2·6H2O and 76.9g SnCl2·2H2O is dissolved in 2000 mL distilled water, and stirring is lower to throw
Plus 200 g atures of coal powdered activated carbons (200 mesh, 450mL), 12 h are impregnated at room temperature.It is under agitation that 16%NaOH is water-soluble
Liquid is slowly added into above-mentioned mixed liquor, and regulation pH value is 6-7, is heated with stirring to boiling, is subsequently cooled to room temperature, is filtered, is washed
Wash to without chlorion and nitrate ion, by solid in 120 DEG C of dryings, obtain catalyst precursor.Catalyst precursor is in nitrogen
Heated up in gas and hydrogen gas mixture, in stablizing at 250 DEG C 2 hours, be continuously heating to 450 DEG C, using 100% pure hydrogen reduction,
Recovery time is 3 hours.Room temperature is down to, with nitrogen displacement, air passivation is introduced, obtains black powder solid catalyst
CAT4。
Hydrogenolysis is still reaction, and C5, C6 sugar alcohol mixtures water that mass percent is 65% are added in a kettle.
Solution, catalyst charge is 8% (mass percent) of amount of sugar alcohol, is 10 with 45% sodium hydrate regulator solution pH value, instead
It is 250 DEG C to answer temperature, and holding Hydrogen Vapor Pressure is 11 MPa, and the reaction time is 2 hours.React after terminating through liquid-phase chromatographic analysis knot
Fruit is as follows：
Embodiment 4
By 300g Ni (NO3)2·6H2O and 90g Sn (NO3)2It is dissolved in 2000 mL distilled water, 200 g is added under stirring
Coconut husk powdered activated carbon (200 mesh, 400mL), impregnates 24 h at room temperature.The 16%NaOH aqueous solution is slowly added under agitation
Enter into above-mentioned mixed liquor, regulation pH value is 6-7, is heated with stirring to boiling, is subsequently cooled to room temperature, filter, washing is to without nitre
Acid ion, by solid in 120 DEG C of dryings, obtains catalyst precursor.Catalyst precursor is in nitrogen and hydrogen gas mixture
Middle heating, in stablizing at 200 DEG C 2 hours, is continuously heating to 400 DEG C, using 100% pure hydrogen reduction, and the recovery time is 2 hours.
Room temperature is down to, with nitrogen displacement, air passivation is introduced, obtains black powder solid catalyst CAT5.
Hydrogenolysis is still reaction, and C5, C6 sugar alcohol mixtures water that mass percent is 55% are added in a kettle.
Solution, catalyst charge is 10% (mass percent) of amount of sugar alcohol, is 10 with 45% sodium hydrate regulator solution pH value, instead
It is 250 DEG C to answer temperature, and holding Hydrogen Vapor Pressure is 10 MPa, and the reaction time is 2 hours.React after terminating through liquid-phase chromatographic analysis knot
Fruit is as follows：
Claims (1)
1. a kind of preparation method of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon binary alcohol catalyst, it is characterised in that including following
Step：
1) quantitative nickel salts, pink salt are weighed and are dissolved in water, 5%~20% aqueous solution is configured to, quantitative activity is then added
High-area carbon, the solid volume ratio of liquid is 1: 1~6: 1, is impregnated 12~24 hours at room temperature, under agitation by 10%~20% sodium hydroxide
The aqueous solution is slowly added into mixed liquor, and regulation pH value is 6~7, and boiling is heated under stirring, room temperature is subsequently cooled to；
2) filter, washing, by solid in 120 DEG C of dryings, obtains catalyst precursor to without chlorion or nitrate ion；
3) catalyst precursor heats up in nitrogen and hydrogen gas mixture, in stablizing at 200~250 DEG C 0.5~2.5 hour,
350~450 DEG C are continuously heating to, using 100% pure hydrogen reduction, the recovery time is 1~3 hour, is down to room temperature, is put with nitrogen
Change, introduce air passivation, obtain black powder solid catalyst；
The catalyst of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol is by absorbent charcoal carrier and 5~50 weight % nickel
And 5~50% the tin of weight constituted, the absorbent charcoal carrier is wood activated charcoal, coal mass active carbon or cocoanut active charcoal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210257996.5A CN102824915B (en) | 2012-07-14 | 2012-07-14 | A kind of catalyst of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210257996.5A CN102824915B (en) | 2012-07-14 | 2012-07-14 | A kind of catalyst of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102824915A CN102824915A (en) | 2012-12-19 |
| CN102824915B true CN102824915B (en) | 2017-11-03 |
Family
ID=47328350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210257996.5A Expired - Fee Related CN102824915B (en) | 2012-07-14 | 2012-07-14 | A kind of catalyst of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102824915B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111375421B (en) * | 2018-12-29 | 2022-10-11 | 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 |
| CN112552528B (en) * | 2020-11-19 | 2022-07-12 | 万华化学集团股份有限公司 | Method for removing solvent in high-temperature-resistant polymer solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502805A (en) * | 2009-03-16 | 2009-08-12 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing acetic anhydride as well as preparation method and application |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5236609A (en) * | 1975-09-16 | 1977-03-22 | Takeda Chem Ind Ltd | Process for preparation of alcohol and carbon monoxide |
-
2012
- 2012-07-14 CN CN201210257996.5A patent/CN102824915B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502805A (en) * | 2009-03-16 | 2009-08-12 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing acetic anhydride as well as preparation method and application |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 多元醇混合物氢解制低碳二元醇催化剂的研究;陈洁静等;《第十五届全国催化学术会议论文集》;20101230;正文第二段和最后一段，表1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102824915A (en) | 2012-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102489315B (en) | Ruthenium catalyst, preparation method and application in synthesizing tetrahydrofurfuryl alcohol | |
| CN102091624B (en) | Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof | |
| CN106083529A (en) | The preparation method of a kind of hydrogenated bisphenol A and bisphenol-A catalyst for hydrogenation | |
| CN102872863B (en) | Carrier type catalyst and application of carrier type catalyst in low-pressure rosin hydrogenation | |
| CN110961110A (en) | Catalyst and application thereof in hydrodechlorination of 2,3, 6-trichloropyridine | |
| CN107739309A (en) | A kind of double carbonylation preparation method of palladium chtalyst acetylene | |
| CN102658207B (en) | High-dispersion palladium catalyst used for anthraquinone hydrogenation and preparation method of same | |
| CN102824915B (en) | A kind of catalyst of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol and preparation method thereof | |
| CN104549254B (en) | Catalyst for preparing 1,6-hexanediol through direct reduction of adipic acid | |
| CN103848720B (en) | A kind of method preparing ethylene glycol | |
| CN109689606A (en) | The method for preparing 1,3- cyclohexanedimethanol | |
| CN109261153B (en) | Supported nickel-based catalyst and preparation method and application thereof | |
| CN104888794B (en) | Metal composition catalyst, preparation method thereof and application thereof in preparation of D, L-menthol | |
| CN101940951B (en) | Load-type chiral catalyst and application thereof in catalysis preparation of Fluoxetine intermediate | |
| CN108607562A (en) | Catalyst and preparation method and application for hexanedioic acid dialkyl ester hexylene glycol | |
| CN102205248A (en) | Preparation method of high-selectivity DSD (4,4'-Diaminodiphenylethylene-2,2'-disulfonic acid) hydrogenation catalyst | |
| CN101209415B (en) | Catalyst for preparing linalyl acetate by hydrogenation of dehydrogenated linalyl acetate | |
| CN109678732B (en) | Method for continuously producing 5-amino-1-pentanol | |
| CN103331160B (en) | Preparation method of high-dispersion copper-based catalyst based on non-precious metal | |
| CN110372516A (en) | A method of preparing cyclohexylamine | |
| CN106423202A (en) | Preparation method of rhodium-ruthenium composite catalyst for preparing ethyl alcohol through acetic acid hydrogenation | |
| CN102836711A (en) | Catalyst for preparing cyclohexene via selective hydrogenation of benzene and preparation method thereof | |
| CN104844539B (en) | A kind of preparation method of piperidines | |
| CN107262092A (en) | A kind of catalyst of the butylene of 1,1,1,4,4,4 hexafluoro of synthesizing cis 2 and its production and use | |
| CN102633648B (en) | Preparation method of n-butylamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171103 Termination date: 20210714 |