CN101768050A - Method for preparing ethylene glycol and 1,2-propylene glycol - Google Patents
Method for preparing ethylene glycol and 1,2-propylene glycol Download PDFInfo
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- CN101768050A CN101768050A CN200910244031A CN200910244031A CN101768050A CN 101768050 A CN101768050 A CN 101768050A CN 200910244031 A CN200910244031 A CN 200910244031A CN 200910244031 A CN200910244031 A CN 200910244031A CN 101768050 A CN101768050 A CN 101768050A
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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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a method for preparing ethylene glycol and 1,2-propylene glycol. In the method, fiber is placed into water to react under the action of a catalyst at the temperature of 200-250 DEG C to obtain the ethylene glycol and the 1,2-propylene glycol. In the method, the fiber is hydrolyzed in hot water; on one hand, the WO3 catalyst, the load WO3 catalyst and the Ru/C catalyst are led into for providing acidity for promoting the acid hydrolysis of the fiber, on the other hand, the intermediate products in the hydrolysis can be inverted into low-carbon matters, and hydrogenation is carried out, so as to obtain the ethylene glycol and the 1,2-propylene glycol. The method has simple process, quick reaction, high efficiency and less energy and is easy for industrialization; no liquid acid is added, and no waste acid is discharged, therefore, the method is environmentally friendly. The method has low requirement on equipment, can not cause the corrosion of the equipment and has small investment; moreover, the inversion rate of the fiber is 100% high, the yield of the ethylene glycol can reach 35%, and the yield of the 1,2-propylene glycol can reach 31%; therefore, the method has significant application value.
Description
Technical field
The present invention relates to Mierocrystalline cellulose production field, particularly relate to a kind of Mierocrystalline cellulose that utilizes and produce ethylene glycol and 1, the method for 2-propylene glycol.
Background technology
Biomass are considered to can substitute future the energy and the chemical source of fossil resource as a kind of renewable resources of extensive existence.In the biomass, cellulose comprises major portion, its effective conversion is the important content that biomass are utilized, and is the following committed step that substitutes fossil resource.Mierocrystalline cellulose is the polymer that glucose aggregates into by glycosidic link, is the plateform molecules of small molecular weight with its depolymerization, the feasible way that they to be converted into other useful chemical again are cellulose conversion.
Polyvalent alcohol is regarded as the important plateform molecules of a class of cellulose conversion, and few from the method for the synthetic polyvalent alcohol of Mierocrystalline cellulose at present, this field demands urgently widening.Existent method mainly concentrates in the production of six carbon polyols such as sorbyl alcohol and N.F,USP MANNITOL, comprise and utilize the mineral acid hydrolysis Mierocrystalline cellulose Ru/C hydrogenation that is coupled again, with noble metal catalyst hydrocelluloses such as solid acid supporting Pt, Ru, the original position protonic acid hydrocellulose that produces with the near-critical water methods such as Ru/C hydrogenation that are coupled again.In addition, also have, utilize the wolfram varbide (W that supports from Mierocrystalline cellulose
2C) and nickel (Ni) catalyzer obtain the method for ethylene glycol, but it is considerably less similarly to obtain the method for low-carbon (LC) (carbon number is less than six) polyvalent alcohol, and obtains 1, the report of 2-propylene glycol did not also have.
Summary of the invention
The purpose of this invention is to provide a kind of production ethylene glycol and 1, the method for 2-propylene glycol.
Production ethylene glycol provided by the invention and 1, the method for 2-propylene glycol comprises the steps: to place water to react Mierocrystalline cellulose under the effect of catalyzer, and reaction finishes and obtains described ethylene glycol and 1, the 2-propylene glycol.
In this method, described catalyzer is made up of component A and B component; Described component A is activated carbon loaded Ru catalyzer (Ru/C), and B component is WO
3Or loading type WO
3The charge capacity (charge capacity is meant the mass ratio of Ru and support C) of described activated carbon loaded Ru catalyzer is 1-4%, specifically can be 1%, 2%, 3%, 4% or 2-4%; Described WO
3Be block WO
3Or powdery WO
3Described loading type WO
3Carrier be activated carbon, aluminum oxide, silicon-dioxide, zirconium dioxide, titanium dioxide or cerium dioxide, described loading type WO
3Charge capacity (charge capacity is meant WO
3Mass ratio with carrier) is 0.1%-70%, specifically can be 0.1-50%, 0.5-60%, 10-60%, 20-70%, 30-60%, 1.0-15%, 5.0-20% or 35-65%, preferred 0.5-20% and 40%-60%; Described Mierocrystalline cellulose is selected from least a in Microcrystalline Cellulose and the natural cellulose.In this method, described catalyst consumption is the 5-500% of described Mierocrystalline cellulose quality, specifically can be 5-100%, 10-200%, 100-500%, 200-450%, 250-400% or 300-400%; Institute's water consumption does not limit, can the submergence Mierocrystalline cellulose and catalyzer get final product.
The temperature that above-mentioned Mierocrystalline cellulose and catalyzer react in water is 200-270 ℃, specifically can be 200-260 ℃, 210-265 ℃, 230-270 ℃ or 240-265 ℃, preferred 250 ℃, the time of reaction is 0.5-5 hour, preferred 0.5 hour, the pressure of reaction is 20-80atm, specifically can be 20-70atm, 30-80atm, 40-70atm or 50-60atm, preferred 80atm.
The invention provides a kind of directly from Mierocrystalline cellulose direct hydrolysis production ethylene glycol and 1, the method for 2-propylene glycol.This method is a hydrocellulose under hot water conditions, by introducing WO
3, loading type WO
3With the Ru/C catalyzer, provide acid on the one hand, promote the cellulosic acid hydrolysis, the intermediate product with hydrolysis is converted into low carbon species on the other hand, and hydrogenation obtains ethylene glycol and 1, the 2-propylene glycol.Method provided by the invention, technology is simple, is swift in response, and is energy-efficient, is easy to industrialization; Do not need to add liquid acid, no spent acid discharging is a kind of environmental protection production method.This method is low for equipment requirements, and equipment is not had corrosion, invests little; Cellulose conversion rate height can reach 100%, and the productive rate of ethylene glycol can reach 35%, 1, and the 2-propylene glycol can reach 31%, has important use and is worth.
Embodiment
Method among the following embodiment if no special instructions, is ordinary method.
Embodiment 1, hydrocellulose are produced ethylene glycol and 1,2-propylene glycol
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reactor of the water (40ml) that capacity is housed, add the 0.3g charge capacity and be 6% WO
3/ C catalyzer and 0.1g charge capacity are 3% Ru/C catalyzer, charge into H
2, making the pressure in the reactor is 80atm, is heated to 240 ℃, reacts 30 minutes.
According to following method, the transformation efficiency of detection fibers element and ethylene glycol and 1, the productive rate of 2-propylene glycol:
With not reacted cellulosic on balance the weighing quality, be 0g.Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Shimadazu LC-20A HPLC; Separator column is: BioRad Carbonhydrate HPX-87C; Analysis condition: moving phase is water: acetonitrile (3: 2), 65 ℃, 0.3ml/min) result shows on high-efficient liquid phase analysis, the retention time at two peaks that reaction product provides is with ethylene glycol and 1, and the retention time at two peaks that 2-propylene glycol standard provides on liquid chromatography is identical, and (retention time that ethylene glycol goes out the peak is: 8.9min, 1, the retention time that the 2-propylene glycol goes out the peak is: 7.9min), be 0.38g ethylene glycol quantitatively, 0.12g 1, the 2-propylene glycol.Calculate the cellulose conversion rate according to the following equation, the productive rate of reaction product.
The result shows that Mierocrystalline cellulose mainly is converted into ethylene glycol and 1, the 2-propylene glycol.The cellulose conversion rate is 100%; Glycol selectivity is 35%, 1, and 2-propylene glycol selectivity is 14%; The ethylene glycol productive rate is 35%, 1, and 2-propylene glycol productive rate is 14%; Other low amounts of product are other polyalcohols materials such as sorbyl alcohol, N.F,USP MANNITOL, glycerine.
The cellulose conversion rate is calculated:
Wherein, the Mierocrystalline cellulose quality=Mierocrystalline cellulose of the conversion quality-Mierocrystalline cellulose residual mass that feeds intake
Ethylene glycol and 1, the selectivity of 2-propylene glycol calculate (the selectivity definition is, under same unit representation, the ratio of product amount and the material quantity that has transformed, this carbon content of sentencing separately is a benchmark):
Ethylene glycol and 1, the calculation of yield of 2-propylene glycol:
Embodiment 2, hydrocellulose are produced ethylene glycol and 1,2-propylene glycol
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reactor of the water (40ml) that capacity is housed, add the 3.0g charge capacity and be 0.5% WO
3/ C catalyzer and 0.1g charge capacity are 3% Ru/C catalyzer, charge into H
2, making the pressure in the reactor is 80atm, is heated to 250 ℃, reacts 30 minutes.
According to following method, the transformation efficiency of detection fibers element and ethylene glycol and 1, the productive rate of 2-propylene glycol:
With not reacted cellulosic on balance the weighing quality, be 0g.Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Shimadazu LC-20A HPLC; Separator column is: BioRad Carbonhydrate HPX-87C; Analysis condition: moving phase is water: acetonitrile (3: 2), 65 ℃, 0.3ml/min) result shows on the high-efficient liquid phase analysis, the retention time at two peaks that reaction product provides is with ethylene glycol and 1, and the retention time at two peaks that 2-propylene glycol standard provides on liquid chromatography is identical, and (retention time that ethylene glycol goes out the peak is: 8.9min, 1, the retention time that the 2-propylene glycol goes out the peak is: 7.9min), be ethylene glycol 0.17g quantitatively respectively, 1,2-propylene glycol 0.29g.Calculate cellulose conversion rate, the transformation efficiency of reaction product and productive rate according to embodiment 1 described formula.
The result shows that Mierocrystalline cellulose mainly is converted into ethylene glycol and 1, the 2-propylene glycol.The cellulose conversion rate is 100%; Glycol selectivity is 15%, 1, and 2-propylene glycol selectivity is 31%; The ethylene glycol productive rate is 15%, 1, and 2-propylene glycol productive rate is 31%; Other low amounts of product are other polyalcohols materials such as sorbyl alcohol, N.F,USP MANNITOL, glycerine.
Embodiment 3, hydrocellulose are produced ethylene glycol and 1,2-propylene glycol
1g Microcrystalline Cellulose (microcrystalline is available from AlfaAesar) is placed the 100ml reactor of the water (40ml) that capacity is housed, add the 0.1g charge capacity and be 50% WO
3/ Al
2O
3Catalyzer and 0.1g charge capacity are 3% Ru/C catalyzer, charge into H
2, making the pressure in the reactor is 80atm, is heated to 250 ℃, reacts 30 minutes.
According to following method, the transformation efficiency of detection fibers element and ethylene glycol and 1, the productive rate of 2-propylene glycol:
With not reacted cellulosic on balance the weighing quality, be 0g.Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Shimadazu LC-20A HPLC; Separator column is: BioRad Carbonhydrate HPX-87C; Analysis condition: moving phase is water: acetonitrile (3: 2), 65 ℃, 0.3ml/min) result shows on the high-efficient liquid phase analysis, the retention time at two peaks that reaction product provides is with ethylene glycol and 1, and the retention time at two peaks that 2-propylene glycol standard provides on liquid chromatography is identical, and (retention time that ethylene glycol goes out the peak is: 8.9min, 1, the retention time that the 2-propylene glycol goes out the peak is: 7.9min), be ethylene glycol 0.28g quantitatively respectively, 1,2-propylene glycol 0.15g.Calculate cellulose conversion rate, the transformation efficiency of reaction product and productive rate according to embodiment 1 described formula.
The result shows that Mierocrystalline cellulose mainly is converted into ethylene glycol and 1, the 2-propylene glycol.The cellulose conversion rate is 100%, and glycol selectivity is 25%, 1, and 2-propylene glycol selectivity is 16%; The ethylene glycol productive rate is 25%, 1, and 2-propylene glycol productive rate is 16%; Other low amounts of product are other polyalcohols materials such as sorbyl alcohol, N.F,USP MANNITOL, glycerine.
Embodiment 4, hydrocellulose are produced ethylene glycol and 1,2-propylene glycol
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reactor of the water (40ml) that capacity is housed, add 0.5g WO
3With the 0.15g charge capacity be 2% Ru/C catalyzer, charge into H
2, making the pressure in the reactor is 80atm, is heated to 205 ℃, reacts 30 minutes.
According to following method, the transformation efficiency of detection fibers element and ethylene glycol and 1, the productive rate of 2-propylene glycol:
With not reacted cellulosic on balance the weighing quality, be 0.75g.Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Shimadazu LC-20A HPLC; Separator column is: BioRad Carbonhydrate HPX-87C; Analysis condition: moving phase is water: acetonitrile (3: 2), 65 ℃, 0.3ml/min) result shows on the high-efficient liquid phase analysis, the retention time at two peaks that reaction product provides is with ethylene glycol and 1, and the retention time at two peaks that 2-propylene glycol standard provides on liquid chromatography is identical, and (retention time that ethylene glycol goes out the peak is: 8.9min, 1, the retention time that the 2-propylene glycol goes out the peak is: 7.9min), be ethylene glycol 0.14g quantitatively respectively, 1,2-propylene glycol 0.02g.Calculate cellulose conversion rate, the transformation efficiency of reaction product and productive rate according to embodiment 1 described formula.
The result shows that Mierocrystalline cellulose mainly is converted into ethylene glycol and 1, the 2-propylene glycol.The cellulose conversion rate is 25%, and glycol selectivity is 50%, 1, and 2-propylene glycol selectivity is 9%; The ethylene glycol productive rate is 12%, 1, and 2-propylene glycol productive rate is 2%, and other low amounts of product are other polyalcohols materials such as sorbyl alcohol, N.F,USP MANNITOL, glycerine.
Embodiment 5, hydrocellulose are produced ethylene glycol and 1,2-propylene glycol
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reactor of the water (40ml) that capacity is housed, add the 0.3g charge capacity and be 6% WO
3/ C catalyzer and 0.75g charge capacity are 4% Ru/C catalyzer, charge into H
2, making the pressure in the reactor is 80atm, is heated to 205 ℃, reacts 5 hours.
According to following method, the transformation efficiency of detection fibers element and ethylene glycol and 1, the productive rate of 2-propylene glycol:
With not reacted cellulosic on balance the weighing quality, be 0.35g.Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Shimadazu LC-20A HPLC; Separator column is: BioRad Carbonhydrate HPX-87C; Analysis condition: moving phase is water: acetonitrile (3: 2), 65 ℃, 0.3ml/min) result shows on the high-efficient liquid phase analysis, the retention time at two peaks that reaction product provides is with ethylene glycol and 1, and the retention time at two peaks that 2-propylene glycol standard provides on liquid chromatography is identical, and (retention time that ethylene glycol goes out the peak is: 8.9min, 1, the retention time that the 2-propylene glycol goes out the peak is: 7.9min), be ethylene glycol 0.26g quantitatively respectively, 1,2-propylene glycol 0.05g.Calculate cellulose conversion rate, the transformation efficiency of reaction product and productive rate according to embodiment 1 described formula.
The result shows that Mierocrystalline cellulose mainly is converted into ethylene glycol and 1, the 2-propylene glycol.The cellulose conversion rate is 65%, and glycol selectivity is 35%, 1, and 2-propylene glycol selectivity is 9%; The ethylene glycol productive rate is 23%, 1, and 2-propylene glycol productive rate is 6%; Other low amounts of product are other polyalcohols materials such as sorbyl alcohol, N.F,USP MANNITOL, glycerine.
Embodiment 6, hydrocellulose are produced ethylene glycol and 1,2-propylene glycol
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reactor of the water (40ml) that capacity is housed, add the 0.1g charge capacity and be 20% WO
3/ C catalyzer and 0.1g charge capacity are 3% Ru/C catalyzer, charge into H
2, making the pressure in the reactor is 20atm, is heated to 205 ℃, reacts 30 minutes.
According to following method, the transformation efficiency of detection fibers element and ethylene glycol and 1, the productive rate of 2-propylene glycol:
With not reacted cellulosic on balance the weighing quality, be 0.75g.Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Shimadazu LC-20A HPLC; Separator column is: BioRad Carbonhydrate HPX-87C; Analysis condition: moving phase is water: acetonitrile (3: 2), 65 ℃, 0.3ml/min) result shows on the high-efficient liquid phase analysis, the retention time at two peaks that reaction product provides is with ethylene glycol and 1, and the retention time at two peaks that 2-propylene glycol standard provides on liquid chromatography is identical, and (retention time that ethylene glycol goes out the peak is: 8.9min, 1, the retention time that the 2-propylene glycol goes out the peak is: 7.9min), be ethylene glycol 0.11g quantitatively respectively, 1,2-propylene glycol 0.03g.Calculate cellulose conversion rate, the transformation efficiency of reaction product and productive rate according to embodiment 1 described formula.
The result shows that Mierocrystalline cellulose mainly is converted into ethylene glycol and 1, the 2-propylene glycol.The cellulose conversion rate is 25%, and glycol selectivity is 43%, 1, and 2-propylene glycol selectivity is 12%; The ethylene glycol productive rate is 11%, 1, and 2-propylene glycol productive rate is 3%, and other low amounts of product are other polyalcohols materials such as sorbyl alcohol, N.F,USP MANNITOL, glycerine.
Embodiment 7,
1g Microcrystalline Cellulose (microcrystalline is available from Alfa Aesar) is placed the 100ml reactor of the water (40ml) that capacity is housed, add the 0.2g charge capacity and be 40% WO
3/ ZrO
2Catalyzer and 0.1g charge capacity are 3% Ru/C catalyzer, charge into H
2, making the pressure in the reactor is 60atm, is heated to 205 ℃, reacts 30 minutes.
According to following method, the transformation efficiency of detection fibers element and ethylene glycol and 1, the productive rate of 2-propylene glycol:
With not reacted cellulosic on balance the weighing quality, be 0.79g.Reaction product is carried out high-efficient liquid phase analysis and quantitative, (Shimadazu LC-20A HPLC; Separator column is: BioRad Carbonhydrate HPX-87C; Analysis condition: moving phase is water: acetonitrile (3: 2), 65 ℃, 0.3ml/min) result shows on the high-efficient liquid phase analysis, the retention time at two peaks that reaction product provides is with ethylene glycol and 1, and the retention time at two peaks that 2-propylene glycol standard provides on liquid chromatography is identical, and (retention time that ethylene glycol goes out the peak is: 8.9min, 1, the retention time that the 2-propylene glycol goes out the peak is: 7.9min), be ethylene glycol 0.07g quantitatively respectively, 1,2-propylene glycol 0.01g.Calculate cellulose conversion rate, the transformation efficiency of reaction product and productive rate according to embodiment 1 described formula.
The result shows that Mierocrystalline cellulose mainly is converted into ethylene glycol and 1, the 2-propylene glycol.The cellulose conversion rate is 21%, and glycol selectivity is 33%, 1, and 2-propylene glycol selectivity is 5%; The ethylene glycol productive rate is 7%, 1, and 2-propylene glycol productive rate is 1%; Other low amounts of product are other polyalcohols materials such as sorbyl alcohol, N.F,USP MANNITOL, glycerine.
Claims (10)
1. produce ethylene glycol and 1 for one kind, the method for 2-propylene glycol comprises the steps: to place water to react Mierocrystalline cellulose under the effect of catalyzer, and reaction finishes and obtains described ethylene glycol and 1, the 2-propylene glycol.
2. method according to claim 1 is characterized in that: described catalyzer is made up of component A and B component; Described component A is activated carbon loaded Ru catalyzer, and B component is WO
3Or loading type WO
3
3. method according to claim 2 is characterized in that: the charge capacity of described activated carbon loaded Ru catalyzer is 1-4%; Described WO
3Be block WO
3Or powdery WO
3Described loading type WO
3Carrier be activated carbon, aluminum oxide, silicon-dioxide, zirconium dioxide, titanium dioxide or cerium dioxide, described loading type WO
3Charge capacity be 0.1%-70%.
4. method according to claim 3 is characterized in that: described loading type WO
3Charge capacity be 0.5-20% or 40-60%.
5. according to the arbitrary described method of claim 1-4, it is characterized in that: described Mierocrystalline cellulose is selected from least a in Microcrystalline Cellulose and the natural cellulose.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: described catalyst consumption is the 5-500% of described Mierocrystalline cellulose quality.
7. according to the arbitrary described method of claim 1-6, it is characterized in that: the temperature of reaction is 200-270 ℃, and the time of reaction is 0.5-5 hour.
8. method according to claim 7 is characterized in that: the temperature of reaction is 250 ℃, and the time of reaction is 0.5 hour.
9. according to the arbitrary described method of claim 1-8, it is characterized in that: the pressure of reaction is 20-80atm.
10. according to the arbitrary described method of claim 1-9, it is characterized in that: the pressure of reaction is 80atm.
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