CN108299154A - A method of chemicals is prepared by xylitol Direct Hydrothermal catalytic hydrogenation - Google Patents
A method of chemicals is prepared by xylitol Direct Hydrothermal catalytic hydrogenation Download PDFInfo
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- CN108299154A CN108299154A CN201810077994.5A CN201810077994A CN108299154A CN 108299154 A CN108299154 A CN 108299154A CN 201810077994 A CN201810077994 A CN 201810077994A CN 108299154 A CN108299154 A CN 108299154A
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- xylitol
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- catalytic hydrogenation
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- hydrothermal catalytic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of method preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, including step：In the reactor, xylitol and water is added, under with the catalyst action for adding hydrogen hydrogenolysis activity, carries out adding hydrogen 30~360min of hydrogenolysis in 423~573K, obtains chemicals.The present invention can be prepared the chemicals of the high added values such as dihydric alcohol by xylitol Direct Hydrothermal Hydrogenation for the method for chemicals, and since this renewable biomass new energy being easily obtained of xylitol is utilized, can realize CO2High-performance bio fix and chemical conversion.
Description
Technical field
The present invention relates to a kind of methods preparing chemicals, more particularly to one kind by xylitol Direct Hydrothermal catalytic hydrogenation
The method for preparing chemicals.
Background technology
Dihydric alcohol is very important polyester-based polymer monomer, can be used for producing unsaturated polyester resin, polyurethane, combustion
Feed additives, surfactant, emulsifier, antifreeze solution of motorcycle etc., most important purposes are production unsaturated-resins (UPR),
China's UPR outputs are 1,700,000 tons within 2010, consume 500,000 tons of dihydric alcohol, wide market.China's dihydric alcohol demand is big
And rely on import more, while petroleum-based production line is difficult to continue；Country's relevant enterprise uses cornstarch for raw material at present
Dihydric alcohol is prepared by the technique of enzyme hydrolysis sugaring, sugar plus hydrogen hydrogenolysis, however is existed " with people by raw material production of chemicals of grain
Strive grain, strive ground with grain " the problem of, development receives serious practical restriction；It is increasingly withered with fossil energies such as crude oil, coals
It exhausts, it is imperative based on the biology base binary alcohol production variation route that reproducible non-grain biomass is raw material.
Xylitol has the characteristics that cheap, abundance, and dihydroxyacetone (DHA) can be obtained through retrograde aldol condensation reaction in it
Or glyceraldehyde, using xylitol as raw material Direct Hydrothermal Hydrogenation production cost can be effectively reduced for dihydric alcohol.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide one kind is urged by xylitol Direct Hydrothermal
Change Hydrogenation for the method for chemicals, this method can prepare the change of high added value by mild controllable hydro-thermal reaction system
Product, and since this renewable biomass new energy being easily obtained of xylitol is utilized, can realize CO2High-performance bio
Fixed and chemical conversion.
In order to achieve the above objects and other related objects, the present invention provides one kind by xylitol Direct Hydrothermal catalytic hydrogenation system
The method of standby chemicals, the method include at least：
Xylitol, water and catalyst are added in the reactor, and carries out adding hydrogen hydrogenolysis under an atmosphere of hydrogen
Product.
A kind of scheme of optimization of the method for chemicals, institute are prepared by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention
It includes copper nickel based metal load type catalyst to state catalyst.
A kind of scheme of optimization of the method for chemicals, institute are prepared by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention
It includes carrier and the active component that is loaded on the carrier to state copper nickel based metal load type catalyst, and the active component includes Cu
One or both of with Ni, the carrier includes ZnO, MgO, La2O3、CeO2、ZrO2One or more of.
The scheme for preparing a kind of optimization of the method for chemicals by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention, with
Calculated on the basis of the integral molar quantity of the copper-nickel Base Metal loaded catalyst, the total load amount of the copper and mickel between 10%~
Between 90%, the molar percentage of the carrier is between 10%~90%.
A kind of scheme of optimization of the method for chemicals, institute are prepared by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention
It includes one kind in batch reactor, flow reactor to state reactor.
A kind of scheme of optimization of the method for chemicals, institute are prepared by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention
The solid-to-liquid ratio of xylitol and water is stated between 1g/100ml~50g/100ml.
A kind of scheme of optimization of the method for chemicals, institute are prepared by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention
The mass ratio of xylitol and the catalyst is stated between 1~5.
A kind of scheme of optimization of the method for chemicals, institute are prepared by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention
It states and adds in hydrogen hydrogenolysis, the pressure of the hydrogen is between 1.0MPa~8.0Mpa.
A kind of scheme of optimization of the method for chemicals, institute are prepared by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention
State plus hydrogen hydrogenolysis in, be additionally added nitrogen as carrier gas, the partial pressure of the nitrogen between 0MPa~7.0Mpa, the hydrogen
Partial pressure is not less than 1.0Mpa.
A kind of scheme of optimization of the method for chemicals, institute are prepared by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention
It states and adds in hydrogen hydrogenolysis, reaction temperature is between 423K~573K.
A kind of scheme of optimization of the method for chemicals, institute are prepared by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention
It states and adds in hydrogen hydrogenolysis, the reaction time is between 30min~360min.
A kind of scheme of optimization of the method for chemicals, institute are prepared by xylitol Direct Hydrothermal catalytic hydrogenation as the present invention
It includes dihydric alcohol of the carbon atom number between 2~5 to state chemicals.
As described above, the method for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation of the present invention, has with following
Beneficial effect：
1, the problem of xylitol raw material sources are extensive, and there is no " striving grain with people ", meets the inherently required of sustainable development.
Dihydroxyacetone (DHA) or glyceraldehyde can be obtained through retrograde aldol condensation reaction in it.It can by the direct chemical synthesis dihydric alcohol of raw material of xylitol
Effectively reduce production cost.
2, " one kettle way " hydro-thermal proposed by the present invention adds hydrogen hydrogenolysis mild condition, high conversion rate, to target product two
The selectivity of first alcohol is good.
3, product of the invention is mainly the dihydric alcohol and important intermediate that carbon atom number is 2~5, dihydric alcohol mainly with
It based on propylene glycol (1,2-PD), is used alone after can detaching, can also be detached without depth and be directly used in production unsaturation
Polyester resin, polyurethane, fuel additive, surfactant, emulsifier, antifreeze solution of motorcycle etc. have many potential uses；
It is widely used as important organic synthesis intermediate.
4, the present invention is that novel, the green and power-economizing method of one kind preparing chemicals, has broad application prospects, is used
It is simple for process, small investment, low energy consumption, yield is high, green non-pollution, technical process is easy to control, can interval and serialization
Operation, catalyst recoverable are suitble to large-scale industrial production.
Description of the drawings
Fig. 1 is the concrete technology schematic diagram for the method that the present invention is prepared chemicals by xylitol Direct Hydrothermal catalytic hydrogenation.
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this specification below by way of specific specific example
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Please refer to attached drawing.It should be noted that the diagram provided in the present embodiment only illustrates the present invention in a schematic way
Basic conception, only display and related component in the present invention rather than component count, shape when according to actual implementation in schema then
Shape and size are drawn, when actual implementation kenel, quantity and the ratio of each component can be a kind of random change, and its component cloth
Office's kenel may also be increasingly complex.
The present invention provide it is a kind of by xylitol be raw material Direct Hydrothermal Hydrogenation for the method for chemicals, process route chart
It can be as shown in Figure 1.The key step of this method is as follows：
Xylitol is added in hydrogenation reactor with water together by a certain percentage, add it is a certain amount of have plus hydrogen hydrogenolysis live
Property catalyst, carry out hydro-thermal catalytic hydrogenation hydrogenolysis, after reaction, product is through a system such as vacuum distillation, rectifying, absorption
After column processing, you can obtain chemicals, such as a variety of glycol products and important intermediate that carbon atom number is 2~5, catalyst
Recyclable regenerative uses after separation is dry, and obtained water can also recycle after chemicals separation.
Below by specific embodiment, the present invention is described further.It should be understood that following embodiment is only used for
The range of the bright present invention rather than limiting the invention.
Embodiment 1
It tests and is carried out in the Parr autoclaves that volume is 100mL, and operate in an intermittent fashion.First in reaction kettle
Middle addition 0.5g xylitols and 50ml deionized waters, solid-to-liquid ratio 1g：100mL.It is 30% to add 0.15g content of metal
Cu-Ni-ZrO2(2:1:7) after catalyst, reaction kettle is sealed, is passed through air in High Purity Hydrogen displacement kettle, and keep Hydrogen Vapor Pressure
It is set as 4MPa, speed of agitator is controlled in 600r/min.After heating starts, temperature is raised to 518K with the rate of 15K/min, reaction
4h stops heating, is cooled to room temperature.The supernatant after centrifugation is taken, 0.22 μm of micro-filtration head is crossed, it is qualitative to carry out GC-MS, GC, HPLC
And quantitative analysis.The solid catalyst isolated is after soaked in absolute ethyl alcohol, the forced air drying 12h in 120 DEG C of baking ovens, and cycle is standby
With.
By the control of gas chromatography mass spectrometry (GC-MS) and standard items GC retention times, hydrogenation liquid phase product is carried out qualitative
Analysis, determines that reaction product is mainly：(small molecular alcohol does not have herein for 1,2- propylene glycol, ethylene glycol and a small amount of small molecule alcohol
Have quantitative).Xylitol conversion rate in solution after reacting total organic carbon (TOC) and the ratio of the carbon in raw material calculated；
Target product yield is the molar ratio of carbon and carbon in raw material in target product, and correlation computations formula is as follows：
With this condition, xylitol hydrothermal conversion rate reaches 97.0%, wherein and 1,2-PD yield reaches 35.0%,
Ethylene glycol is 21.6%.
Embodiment 2
Specific implementation process is such as embodiment 1, except that 10g xylitols and 50mL deionized waters, solid-to-liquid ratio is added
For 20g：100mL, while the Cu-Ni-ZrO that 2.0g content of metal is 30% is added2(2:1:7) catalyst；Reaction temperature is steady
It is scheduled on 523K, reaction time 3h, Hydrogen Vapor Pressure is set in 4MPa.
After reaction, product analysis is learnt, xylitol hydrothermal conversion rate reaches 18.9%, wherein 1,2-PD is received
Rate reaches 7.5%, ethylene glycol 5.6%.
Embodiment 3
For specific implementation process such as embodiment 1, the xylitol quality of different additions is 5g, deionized water 50mL,
Solid-to-liquid ratio is 10g:100mL, while it is the Cu-Ni-ZrO that 1.0g content of metal is 70% that quality, which is added,2(4:3:3) it is catalyzed
Agent；System temperature 423K, reaction time extend to 4h, and Hydrogen Vapor Pressure is set in 6MPa.
After reaction, product analysis is learnt, xylitol hydrothermal conversion rate reaches 70.0%, wherein 1,2-PD is received
Rate reaches 7.8%, ethylene glycol 7.3%.
Embodiment 4
Specific implementation process is such as embodiment 1, except that the xylitol quality being added is 2.5g, deionized water is
50mL, solid-to-liquid ratio 5g:100mL, while it is the Cu-Ni-ZrO that 0.5g content of metal is 80% that quality, which is added,2(5:3:2) it urges
Agent；Reaction temperature maintains 503K, reaction time 2h, and Hydrogen Vapor Pressure is set in 4MPa.
After reaction, product analysis is learnt, xylitol hydrothermal conversion rate reaches 85.9%, wherein 1,2-PD is received
Rate reaches 8.6%, ethylene glycol 8.9%.
Embodiment 5
Specific implementation process is such as embodiment 1, except that the xylitol of 0.5g is added, deionized water 50mL, Gu
Liquor ratio is 1g:100mL, while it is the Cu-Ni-ZrO that 0.15g content of metal is 90% that quality, which is added,2(6:3:1) catalyst；
Reaction temperature maintains 473K, reaction time 2h, and Hydrogen Vapor Pressure is set in 4MPa.
After reaction, product analysis is learnt, xylitol hydrothermal conversion rate reaches 95.3%, wherein 1,2-PD is received
Rate reaches 11.6%, ethylene glycol 9.1%.
Embodiment 6
Specific implementation process is such as embodiment 1, except that the xylitol of 1.0g is added, deionized water 50mL, Gu
Liquor ratio is 2g:100mL, while it is the Ni-ZrO that 0.2g load capacity is 20% that quality, which is added,2(2:8) catalyst；Reaction temperature is tieed up
It holds in 573K, reaction time 2h, Hydrogen Vapor Pressure is set in 6MPa.
After reaction, product analysis is learnt, xylitol hydrothermal conversion rate reaches 97.3%, wherein 1,2-PD is received
Rate reaches 10.6%, ethylene glycol 6.6%.
Embodiment 7
Specific implementation process is such as embodiment 1, except that the xylitol of 1.0g is added, deionized water 50mL, Gu
Liquor ratio is 2g:100mL, while it is the Cu-ZrO that 0.2g load capacity is 20% that quality, which is added,2(2:8) catalyst；Reaction temperature is tieed up
It holds in 573K, reaction time 2h, Hydrogen Vapor Pressure is set in 4MPa.
After reaction, product analysis is learnt, xylitol hydrothermal conversion rate reaches 48.3%, wherein 1,2-PD is received
Rate reaches 23.7%, ethylene glycol 13.0%.
Embodiment 8
Xylitol hydro-thermal catalytic hydrogenation continuous experiment carries out in the trickle bed catalyst test apparatus that volume is 10ml.It is first
It is 1g first to prepare solid-to-liquid ratio:The xylitol solution of 50mL, preparation method are：Xylitol is mixed and shifted with water by a certain percentage
To head tank, it is preheated to 323K.The Cu-Ni-ZrO for being 30% by load capacity2(2:1:7) solid catalyst passes through compression molding,
Broken, precise 10g after sieving, the flat-temperature zone being filled in trickle bed reaction tube carries out evaluation experimental.The carrier gas of experiment is
N2And H2, it is 4MPa to keep total system pressure by adjusting, wherein hydrogen partial pressure 1MPa, nitrogen partial pressure 3Mpa keep hydrogen
Gas velocity is 30mL/min, nitrogen flow rate 50mL/min.Feed pump selects special reciprocating pump in parallel, xylitol solution
The flow speed stability of charging is 2mL/min, and the temperature of catalyst flat-temperature zone is maintained at 573K, after reacting balance, is taken every 15min
Sample is analyzed.Product analysis method is with reference to embodiment 1.
With this condition, xylitol hydrothermal conversion rate reaches 80.2%, wherein and 1,2-PD yield reaches 11.7%,
Ethylene glycol is 7.8%.
In conclusion the present invention provides a kind of method preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation hydrogenolysis,
Five carbon structures of xylitol provide prerequisite for it as preparation biology base dihydric alcohol；In xylitol solution hydrogenation process
Without acid/base and enzyme hydrolysis process, should " one kettle way " simple for process and green non-pollution, feed stock conversion is high and selectivity of product
Good, catalyst renewable use after being simply separated by solid-liquid separation has the advantage and actual application value realized.
So the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (12)
1. a kind of method preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, which is characterized in that the method is at least wrapped
It includes：
Xylitol, water and catalyst are added in the reactor, and carries out that hydrogen hydrogenolysis is added to obtain chemicals under an atmosphere of hydrogen.
2. the method according to claim 1 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, it is characterised in that：
The catalyst includes copper nickel based metal load type catalyst.
3. the method according to claim 2 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, it is characterised in that：
The copper-nickel Base Metal loaded catalyst includes carrier and the active component that is loaded on the carrier, and the active component includes
One or both of Cu and Ni, the carrier include ZnO, MgO, La2O3、CeO2、ZrO2One or more of.
4. the method according to claim 3 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, it is characterised in that：
Calculated on the basis of the integral molar quantity of the copper-nickel Base Metal loaded catalyst, the total load amount of the copper and mickel between 10%~
Between 90%, the molar percentage of the carrier is between 10%~90%.
5. the method according to claim 1 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, it is characterised in that：
The reactor includes one kind in batch reactor, flow reactor.
6. the method according to claim 1 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, it is characterised in that：
The solid-to-liquid ratio of the xylitol and water is between 1g/100ml~50g/100ml.
7. the method according to claim 1 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, it is characterised in that：
The mass ratio of the xylitol and the catalyst is between 1~5.
8. the method according to claim 1 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, it is characterised in that：
In described plus hydrogen hydrogenolysis, the pressure of the hydrogen is between 1.0MPa~8.0Mpa.
9. the method according to claim 1 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, it is characterised in that：
In described plus hydrogen hydrogenolysis, nitrogen is additionally added as carrier gas, the partial pressure of the nitrogen is described between 0MPa~7.0Mpa
The partial pressure of hydrogen is not less than 1.0Mpa.
10. the method according to claim 1 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, feature exist
In：In described plus hydrogen hydrogenolysis, reaction temperature is between 423K~573K.
11. the method according to claim 1 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, feature exist
In：In described plus hydrogen hydrogenolysis, the reaction time is between 30min~360min.
12. the method according to claim 1 for preparing chemicals by xylitol Direct Hydrothermal catalytic hydrogenation, feature exist
In：The chemicals includes dihydric alcohol of the carbon atom number between 2~5.
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| CN201810077994.5A CN108299154A (en) | 2018-01-26 | 2018-01-26 | A method of chemicals is prepared by xylitol Direct Hydrothermal catalytic hydrogenation |
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| US20070293665A1 (en) * | 2005-12-08 | 2007-12-20 | Holcomb Dale E | Catalyst and Method for Production of Polyols by Hydrogenolysis of Carbohydrates |
| CN101613253A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | The catalytic cracking method of a kind of sugar and sugar alcohol |
| CN104119203A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for preparation of dihydric alcohols by catalytic cracking of high carbon polyols under nitrogen atmosphere |
| CN104710277A (en) * | 2013-12-17 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for preparation of low carbon alcohol by hydrogenolysis of sugar and sugar alcohol |
| CN105142776A (en) * | 2013-03-01 | 2015-12-09 | 科莱恩公司 | Catalyst for polyol hydrogenolysis |
| CN105669373A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method for hydrocracking polyols |
-
2018
- 2018-01-26 CN CN201810077994.5A patent/CN108299154A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070293665A1 (en) * | 2005-12-08 | 2007-12-20 | Holcomb Dale E | Catalyst and Method for Production of Polyols by Hydrogenolysis of Carbohydrates |
| CN101613253A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | The catalytic cracking method of a kind of sugar and sugar alcohol |
| CN105142776A (en) * | 2013-03-01 | 2015-12-09 | 科莱恩公司 | Catalyst for polyol hydrogenolysis |
| CN104119203A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for preparation of dihydric alcohols by catalytic cracking of high carbon polyols under nitrogen atmosphere |
| CN104710277A (en) * | 2013-12-17 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for preparation of low carbon alcohol by hydrogenolysis of sugar and sugar alcohol |
| CN105669373A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method for hydrocracking polyols |
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Application publication date: 20180720 |