CN109748777A - A kind of method that 1,2,6- hexanetriol catalytic hydrogenolysis prepares 1,6-HD - Google Patents
A kind of method that 1,2,6- hexanetriol catalytic hydrogenolysis prepares 1,6-HD Download PDFInfo
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- CN109748777A CN109748777A CN201811599390.3A CN201811599390A CN109748777A CN 109748777 A CN109748777 A CN 109748777A CN 201811599390 A CN201811599390 A CN 201811599390A CN 109748777 A CN109748777 A CN 109748777A
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Abstract
The present invention provides a kind of methods that 1,2,6- hexanetriol catalytic hydrogenolysis prepares 1,6-HD.This method, for raw material, passes through a step catalytic hydrogenolysis process with 1,2,6- hexanetriol under the conditions of existing for catalyst, the solid acid, realize 1,2,6- hexanetriol high conversion, in high yield preparation 1,6- hexylene glycol.The characteristics of technology path provided by the present invention short, feed stock conversion and 1 with the reaction time, 6- hexylene glycol high income, and raw material can be obtained from reproducible biomass resource, have the advantages that not depending on fossil resource.
Description
Technical field
The invention belongs to the preparation field of biomass trans-utilization and fine chemicals, specifically a kind of biomass is come
The method that the 1,2,6- hexanetriol catalytic hydrogenolysis in source prepares 1,6-HD.
Background technique
1,6- hexylene glycol is a kind of important fine chemistry industry material, is had in fields such as polyester, coil coating, light curing agents
Important application.
1,6- hexylene glycol manufacturing method more mature at present is with 1,6- adipic acid for raw material, and it is anti-that esterification occurs with methanol
Dimethyl adipate should be generated, then hydrogenated obtains 1,6- hexylene glycol.As United States Patent (USP) US3268588 disclose it is a kind of by penta 2
The mixture of carboxylic acids such as acid, adipic acid, 6 hydroxycaproic acid are esterified, and hydrogenate obtain 1,6- hexylene glycol later, are then carried out again
Distillation separation.Chinese patent CN1594252A discloses one kind using adipic acid as raw material, prepares adipic acid through high pressure esterification, separation
Dimethyl ester.Again using dimethyl adipate as raw material, using noble metals such as Pt, Pd, Ru as catalyst to catalyzing hydrogenating prepare 1,6- oneself
Glycol.It is simultaneously then directly to add hydrogen to prepare 1,6-HD with dimethyl adipate in Chinese patent CN101113128A.Instead
Answer pressure 7MPa, 300 DEG C of temperature, air speed 0.2h-1.However all exist in above method raw material is non-renewable, product yield is low,
By-product separates the disadvantages of difficult more.
The important source of 1,2,6- hexanetriol is exactly to be obtained by biomass-based 5 hydroxymethyl furfural (HMF) catalytic hydrogenolysis
It arrives.Lenno NIVEA Corp, the U.S. realized in disclosed patent CN201580067986.7 catalyzed conversion HMF to 1,2,6- oneself
Triol；Patent CN201180036114.6, which is reported, is converted to oxinane -2- methanol for 5 hydroxymethyl furfural, then again by four
Hydrogen pyrans -2- methanol is converted into 1,2,6- hexanetriol.1,2,6- hexanetriol is similar with 1,6-HD chemical structure, element forms
It is close, if it is possible to by secondary hydroxyl selective removal in 1,2,6- hexanetriol molecule, so that it may obtain 1,6- hexylene glycol, establish with
Biomass resource is the brand new technical route that final raw material prepares 1,6-HD.
Summary of the invention
The purpose of the present invention is to provide the method that one kind prepares 1,6- hexylene glycol with 1,2,6- hexanetriol for raw material, this sides
Method is easy to operate, the conversion ratio of raw material and 1, the high income of 6- hexylene glycol, and by-product is less.
Technical solution of the present invention are as follows:
The method that one kind 1,2,6- hexanetriol catalytic hydrogenolysis prepares 1,6- hexylene glycol is that reaction is former with 1,2,6- hexanetriol
Material, carries out catalytic hydrogenolytic cleavage in autoclave；The active component of reacting middle catalyst is nickel, in ruthenium, rhodium, palladium, iridium, platinum
One or more, load capacity of the active component on carrier is 1-10wt% in catalyst；The dosage of catalyst is 1,
The 1-50% of 2,6- hexanetriol quality；Reaction carries out in presence of hydrogen, and reaction Hydrogen Vapor Pressure is 0.5-8MPa, and reaction temperature is
60-240 DEG C, reaction time 0.5-12h.
Be additionally added solid acid in above-mentioned reaction system, solid acid be wolframic acid, silico-tungstic acid, phosphotungstic acid, phosphomolybdic acid one kind or
It is two or more；The dosage of solid acid is 50% or less 1,2,6- hexanetriol quality.
It further include co-catalyst in above-mentioned catalyst, co-catalyst and active component all load on carrier, co-catalyst
Molar ratio with active component is 1.0 or less；The co-catalyst is one or both of zinc, magnesium, vanadium, manganese, molybdenum, tungsten, rhenium
More than.
Before above-mentioned catalyst is for preparation 1, the 6- hexylene glycol reaction of 1,2,6- hexanetriol catalytic hydrogenolysis, which is carried out
Pretreatment: 0.5-6h is restored at 200-500 DEG C in atmosphere of hydrogen.
Further, above-mentioned carrier is the Al in metal oxide2O3、TiO2、ZrO2、SiO2、Nb2O5、SnO2Or active carbon
One of.
Further, the reaction dissolvent of above-mentioned catalytic hydrogenolytic cleavage is one of water, propyl alcohol, methanol, ethyl alcohol, isopropanol
Or it is two or more；The mass concentration of 1,2,6- hexanetriol is 5-20% in reaction system.
Still more preferably, the reaction pressure of above-mentioned catalytic hydrogenolytic cleavage is 1-6MPa, and temperature is 80-180 DEG C, when reaction
Between be 1-8h.
The present invention has the advantage that
1. this process has raw material compared with the prior art with 1,2,6- hexanetriol of biomass catalyzing converted product for raw material
The advantages that resource is renewable, meets the requirement of Green Chemistry and sustainable development.
2. the high conversion rate of 1,2,6- hexanetriols, the high income of 1,6- hexylene glycol, reaction time under this composite catalyst
Short, reaction condition is mild.
Specific embodiment
Embodiment 1
The preparation of catalyst and catalytic hydrogenolysis experiment
Catalyst is prepared using infusion process, and carrier is nano zirconium dioxide, the aqueous solution incipient impregnation of metal salt, dipping
Dry 12h at 110 DEG C afterwards, then roasts 3h, reductase 12 h in last 300 DEG C of atmosphere of hydrogen in 350 DEG C of air atmospheres.Active carbon is
When carrier, air atmosphere is changed to high pure nitrogen, other conditions with it is as before.Then a certain amount of 1,2,6- hexanetriol, anti-is taken
It answers solvent and catalyst and solid acid in 25mL stainless steel cauldron, is passed through certain pressure hydrogen and replaces sky in kettle repeatedly
Gas.It is warming up to assigned temperature reaction certain time.Reaction kettle is cooled down after reaction to room temperature, finally filter and to reaction solution into
Row chromatography.
Embodiment 2
1,2,6- hexanetriol catalytic hydrogenolysis systems 1 on one different activities metallic catalyst of table, 6- hexylene glycol result (160 DEG C,
1MPa H2, solvent is 2mL water, and 1,2,6- hexanetriol dosage is 5mmol, and the load capacity of active component is 5wt%, co-catalyst:
Active component=1, catalyst amount 5wt%, phosphotungstic acid dosage are 5wt%, reaction time 2h)
It is Re that optimum activity group, which is divided into the best co-catalyst of Ru, as can be seen from Table I.With Ru-ReOx/ZrO2For catalyst
When substrate convert completely, the yield 97 of 1,6- hexylene glycol.Followed by when with Ru/ZrO2Substrate also converts completely when for catalyst,
The yield of 1,6-HD is 95%.It is Ru/ZrO in view of testing used catalyst below economy problems2。
Embodiment 3
1,2,6- hexanetriol catalytic hydrogenolysis systems 1 on two different catalysts carrier of table, 6- hexylene glycol result (160 DEG C, 1MPa
H2, solvent is 2mL water, and 1,2,6- hexanetriol dosage is 5mmol, and Ru load capacity is 5wt%, catalyst amount 5wt%, phosphorus tungsten
Sour dosage is 5wt%, reaction time 2h)
By table two it can be seen that the optimum carrier of active component is ZrO under the conditions of equivalent responses2, 1,2,6- hexanetriol at this time
The yield that selects of conversion completely, 1,6- hexylene glycol is 98%.
Embodiment 4
Table 3 is in Ru/SiO2Added on catalyst different solid acids to 1,2,6- hexanetriol catalytic hydrogenolysis 1,6- oneself two
(160 DEG C, 1Mpa, 2h, solvent is 2mL water, and 1,2,6- hexanetriol dosage is 5mmol, and Ru load capacity is for the influence of the result of alcohol
5wt%, catalyst amount 5wt%, solid acid dosage are 5wt%).
It can be seen from Table 3 that the addition of phosphotungstic acid and Amberlyst-15 can be such that 1,2,6- hexanetriol turns completely
Change, and 1, the 6- hexylene glycol of high yield can be obtained, but the high-temperature resistance of Amberlyst-15 is poor here that we are preferably
Phosphotungstic acid.
Embodiment 5
Table four is in Ru/Al2O3The knot of differential responses time 1,2,6- hexanetriol catalytic hydrogenolysis 1,6-HD on catalyst
Fruit (160 DEG C, 1Mpa H2, solvent is 2mL water, and 1,2,6- hexanetriol dosage is 5mmol, and Ru load capacity is 5wt%, and catalyst is used
Amount is 5wt%, and phosphotungstic acid dosage is 5wt%).
By table four it can be seen that in Ru/Al2O3Optimum reacting time is 4h on catalyst, and 1,2,6- hexanetriols are complete at this time
Full conversion, the yield of 1,6- hexylene glycol have reached 97%.As the yield of the increase 1,6-HD in reaction time is first stable again
Reduce, the yield of n-hexyl alcohol gradually increases.
Embodiment 6
The 1,2,6- hexanetriol catalytic hydrogenolysis 1,6-HD under differential responses pressure on Ru/ZSM-5 catalyst of table five
Result (160 DEG C, 2h, solvent be 2mL water, 1,2,6- hexanetriol dosage be 5mmol, Ru load capacity be 5wt%, catalyst use
Amount is 5wt%, and phosphotungstic acid dosage is 5wt%).
By table five it can be seen that optimum response pressure be 1Mpa, at this time 1,2,6- hexanetriol conversion ratios be 92%, 1,6- oneself
The yield of glycol is 94%.Simultaneously it can be seen that the variation of pressure influences reaction being not very greatly that we preferably react here
Pressure is 1Mpa.
Embodiment 7
Table six is in Rh-Re/ZrO2On catalyst at a temperature of differential responses 1,2,6- hexanetriol catalytic hydrogenolysis 1,6- oneself two
(1Mpa, 2h, solvent are 2mL water to the result of alcohol, and 1,2,6- hexanetriol dosage is 5mmol, and Ru load capacity is 5wt%, and catalyst is used
Amount is 5wt%, and phosphotungstic acid dosage is 5wt%)
By table six it can be seen that the conversion ratio of 1,2,6- hexanetriol as the temperature rises gradually increase it is complete at 160 DEG C
Full conversion, the yield of 1,6- hexylene glycol is 98% at this time.The yield for continuing to increase temperature 1,6-HD reaches maximum at 180 DEG C
Then it is gradually reduced.In view of energy consumption problem optimal reaction temperature is 160 DEG C.
Embodiment 8
Table seven is in Ru/SnO2Result of the different solvents to 1,2,6- hexanetriol catalytic hydrogenolysis 1,6-HD on catalyst
Influence (160 DEG C, 1Mpa, 2h, solvent be 2mL water, 1,2,6- hexanetriol dosage be 5mmol, Ru load capacity be 5wt%, catalysis
Agent dosage is 5wt%, and phosphotungstic acid dosage is 5wt%).
Optimal reaction result has been obtained when we can see that water+tetrahydrofuran is as solvent by table 7.
Embodiment 9
Table 8 is in Ru/ZrO2Different catalysts dosage is to 1,2,6- hexanetriol catalytic hydrogenolysis 1,6-HD on catalyst
The influence of result (160 DEG C, 1Mpa, 2h, solvent is 2mL water, and 1,2,6- hexanetriol dosage is 5mmol, and Ru load capacity is
5wt%, phosphotungstic acid dosage are 5wt%).
By table eight it can be seen that as first stable rear reduction is presented in the yield of the increase 1,6-HD of catalyst amount
Trend, when catalyst amount be greater than 20wt% when n-hexyl alcohol yield start to increase, finally tend towards stability.Therefore available
Optimum catalyst dosage is 5wt%.
Embodiment 10
Table nine is in Ru-ReOx/ZrO2Different solid acid dosages are to 1,2,6- hexanetriol catalytic hydrogenolysis 1,6- on catalyst
(160 DEG C, 1Mpa, 2h, solvent is 2mL water, and 1,2,6- hexanetriol dosage is 5mmol, Ru load capacity for the influence of the result of hexylene glycol
For 5wt%, catalyst amount 5wt%).
Can be seen that the increase by 1 with solid acid dosage by table nine, the selectivity of 6- hexylene glycol first increases to be reduced afterwards, when
Solid acid dosage begins with oxinane -2- methanol when being 10wt% occurs and gradually increases with the increase of solid acid dosage
Add.It can be seen that the optimum amount of solid acid is 5wt%.
Embodiment 11
Table ten is in Ru/ZrO2Different concentration of substrate are to 1,2,6- hexanetriol catalytic hydrogenolysis 1,6-HD on catalyst
As a result (160 DEG C, 1Mpa, 2h, solvent is 2mL water, and Ru load capacity is 5wt%, catalyst amount 5wt%, solid acid for influence
Dosage is 5wt%).
By table ten it can be seen that gradually decreasing with the conversion ratio of 1,2, the 6- hexanetriol of increase of concentration of substrate, 1,6- oneself
The yield of glycol is first increased and is finally tended towards stability.Therefore available substrate optium concentration is 10wt%.
For being familiar with person skilled in the art of the present invention in the technical scope that the present invention reports, change can be readily occurred in
Change or replace, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention is not limited only to the above implementation
Example, it should be subject to the protection scope in claims.
Claims (8)
1. one kind 1,2, the method that 6- hexanetriol catalytic hydrogenolysis prepares 1,6- hexylene glycol, it is characterised in that: with 1,2,6- hexanetriol
For reaction raw materials, catalytic hydrogenolytic cleavage is carried out in autoclave；The active component of reacting middle catalyst be nickel, ruthenium, rhodium,
One or more of palladium, iridium, platinum, load capacity of the active component on carrier is 1-10wt% in catalyst；Catalyst
Dosage be 1,2,6- hexanetriol quality 1-50%；Reaction carries out in presence of hydrogen, and reaction Hydrogen Vapor Pressure is 0.5-8MPa,
Reaction temperature is 60-240 DEG C, reaction time 0.5-12h.
2. according to the method described in claim 1, it is characterized by: be additionally added solid acid in reaction system, solid acid be wolframic acid,
The one or more of silico-tungstic acid, phosphotungstic acid, phosphomolybdic acid；The dosage of solid acid be 1,2,6- hexanetriol quality 50% with
Under.
3. method according to claim 1 or 2, it is characterised in that: further include co-catalyst, co-catalysis in the catalyst
Agent and active component all load on carrier, and the molar ratio of co-catalyst and active component is 1.0 or less；The co-catalyst is
One or more of zinc, magnesium, vanadium, manganese, molybdenum, tungsten, rhenium.
4. method according to claim 1 or 2, it is characterised in that: the catalyst is catalyzed hydrogen for 1,2,6- hexanetriols
Before solution preparation 1,6- hexylene glycol reaction, which is pre-processed: restoring 0.5- at 200-500 DEG C in atmosphere of hydrogen
6h。
5. according to the method described in claim 3, it is characterized by: the catalyst is used for 1,2,6- hexanetriol catalytic hydrogenolysis systems
Before standby 1,6- hexylene glycol reaction, which is pre-processed: restoring 0.5-6h at 200-500 DEG C in atmosphere of hydrogen.
6. method described according to claim 1 or 2 or 5, it is characterised in that: the carrier is the Al in metal oxide2O3、
TiO2、ZrO2、SiO2、Nb2O5、SnO2Or one of active carbon.
7. method described according to claim 1 or 2 or 5, it is characterised in that: the reaction dissolvent of the catalytic hydrogenolytic cleavage is
One or more of water, propyl alcohol, methanol, ethyl alcohol, isopropanol；The mass concentration of 1,2,6- hexanetriol is in reaction system
5-20%.
8. method described according to claim 1 or 2 or 5, it is characterised in that: the reaction pressure of catalytic hydrogenolytic cleavage is 1-
6MPa, temperature are 80-180 DEG C, reaction time 1-8h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110694686A (en) * | 2019-11-08 | 2020-01-17 | 西安凯立新材料股份有限公司 | Method for preparing phosphotungstic acid modified activated carbon supported palladium catalyst and application |
| CN114478408A (en) * | 2022-01-24 | 2022-05-13 | 上海巽田科技股份有限公司 | Method for continuously synthesizing homopiperazine |
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| CN110694686A (en) * | 2019-11-08 | 2020-01-17 | 西安凯立新材料股份有限公司 | Method for preparing phosphotungstic acid modified activated carbon supported palladium catalyst and application |
| CN110694686B (en) * | 2019-11-08 | 2022-08-16 | 西安凯立新材料股份有限公司 | Method for preparing phosphotungstic acid modified activated carbon supported palladium catalyst and application |
| CN114478408A (en) * | 2022-01-24 | 2022-05-13 | 上海巽田科技股份有限公司 | Method for continuously synthesizing homopiperazine |
| CN114478408B (en) * | 2022-01-24 | 2023-10-24 | 上海巽田科技股份有限公司 | Method for continuously synthesizing homopiperazine |
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