CN103897716B - A kind of method utilizing Dextrose production liquid fuel - Google Patents
A kind of method utilizing Dextrose production liquid fuel Download PDFInfo
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- CN103897716B CN103897716B CN201210571108.7A CN201210571108A CN103897716B CN 103897716 B CN103897716 B CN 103897716B CN 201210571108 A CN201210571108 A CN 201210571108A CN 103897716 B CN103897716 B CN 103897716B
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- liquid fuel
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- glucose
- acetone
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The present invention relates to a kind of novel method utilizing Dextrose production liquid fuel.Method of the present invention utilizes glucose pre-press in the basic conditions, then the mixture base catalysis pyrolysis obtained is produced the mixture of the liquid fuels such as acetone, Virahol, butanols, butanone and ethanol.Method choice of the present invention is high, and process is simple, is easy to control, and principal product is easy to be separated, and by-product liquid fuel, organism utilization rate is high, has very high economic worth and prospects for commercial application.
Description
Technical field
The invention belongs to a kind of novel method utilizing Dextrose production liquid fuel, the method is applicable to utilizing glucose alkalescence catalytic pyrolysis preparing to get liquid fuel.
Background technology
Acetone, Virahol, butanone, butanols and ethanol are all important organic solvent and industrial chemicals, are widely used in explosive, plastics, pharmacy and the industry such as synthetic glass, synthetic rubber.Acetone is important organic synthesis raw material, and for the production of epoxy resin, polycarbonate, synthetic glass etc. are also good solvents, are also used as thinner, clean-out system, extraction agent.Virahol is important Chemicals and raw material, for pharmacy, makeup, plastics, spices, coating etc.Butanone is mainly used as solvent, or preparation medicine, dyestuff, washing composition, spices, antioxidant and some catalyzer is intermediate.Butanols is for the manufacture of methylethylketone, the raw material of compound essence, dyestuff etc., and be also used as solvent, the vapor pressure of butanols is low, and corrodibility is less is biofuel of new generation.Ethanol is good organic solvent and sterilizing agent.
Before the early 1990s in last century, the synchronous production of acetone, butanols and ethanol mainly utilizes grain fermentative production, from the nineties, is replaced by petrochemical complex method.Now along with the exhaustion day by day of petroleum resources and the day by day serious of environmental problem, new method production acetone, butanols and ethanol is adopted to cause the extensive concern of countries in the world.
Chinese patent CN101161818A proposes a kind of method adopting B-Starch from Wheat replacement of corn fermentation production of acetone-butanol.It is raw material that Chinese patent CN101363031 proposes with maize peel, carries out the production method of acetone-butanol through the process such as steaming and decocting under high pressure, enzymatic saccharification.Chinese patent CN101358218A proposes a kind of method utilizing stalk coproduction xylose production acetone-butanol, and the method utilizes xylose residue to be hydrolyzed to glucose under the effect of cellulase, utilizes glucose fermentation to produce acetone-butanol.Chinese patent CN102352381A propose a kind of with xylose production waste liquid for raw material, utilize microbial fermentation technology bio-transformation sugar source production chemical product acetone-butanol.Chinese patent CN102286549A proposes a kind of with the method for cellobiose, xylose and glucose mixing sugar fermentation production of acetone-butanol.
Above-mentioned method is all based on biofermentation technique, and the production concentration of biological fermentation is low, and the energy that enriching and purifying needs is very large, and the cycle used of fermenting is very long, does not utilize the production of bulk chemical.
Therefore need the novel method researching and developing a kind of preparing liquid fuel, the method should have the shorter reaction cycle, and production concentration is high and should be easy to separation and purification.
Summary of the invention
For overcoming the problems of the prior art, the object of this invention is to provide a kind of novel method utilizing Dextrose production liquid fuel, the method is short for reaction time, and production concentration is higher, and is easy to separation and purification.
Therefore, the invention provides and a kind ofly utilize the method for Dextrose production liquid fuel (below sometimes referred to as " method of the present invention "), said method comprising the steps of: by glucose feed and excessive basic catalyst (namely, basic catalyst is greater than 1 with the mol ratio of glucose feed) mix after add tank reactor, pre-treatment is carried out under the pressure of the temperature of 100 DEG C ~ 250 DEG C and 0.1MPa ~ 4.0MPa, mixture pre-treatment obtained and excessive basic catalyst are (namely, basic catalyst is greater than 1 with the mol ratio of glucose feed in mixture) mix after add tubular reactor, at rare gas element, under the atmosphere of water vapour or both mixed gass and at 140 DEG C ~ 700 DEG C, the heating temperatures reaction 0.1hr ~ 2hr of preferably 300 DEG C ~ 700 DEG C, preferred 1h ~ 2h, collect the product liquid be obtained by reacting, described product liquid comprises liquid fuel.
In the method for the invention, glucose feed and basic catalyst all can add in solid form, such as, directly with commercially available raw material form, or after suitable pulverizing or grinding plant process, make powder or particle form interpolation.If with powder or particle form charging, then its granularity is unrestricted, as long as be convenient to reactor charging and mutually mix.
In the preferred embodiment of method of the present invention, basic catalyst can be the mixture of a kind of in the oxide compound of basic metal or alkaline-earth metal or oxyhydroxide or any two kinds.
In a preferred embodiment of method of the present invention, basic metal can be sodium, preferably uses its oxyhydroxide, i.e. sodium hydroxide.
In a preferred embodiment of method of the present invention, alkaline-earth metal can be calcium, preferably uses its oxide compound, i.e. calcium oxide.
In the further preferred embodiment of method of the present invention, when basic catalyst is the mixture of calcium oxide and sodium hydroxide, the mol ratio of calcium oxide and sodium hydroxide can be 1: 1 ~ 1: 5.
In the preferred embodiment of method of the present invention, the pretreated time can be 1hr ~ 10hr.
In the preferred embodiment of method of the present invention, rare gas element can be nitrogen.
In the method for the invention, the liquid fuel comprised in product liquid can be the mixture of the products such as acetone, Virahol, butanone, butanols and ethanol, and the respective content ratio of often kind of liquid fuel and distribution can change according to the difference of operational condition.
In the present invention, pretreated reactor can adopt tank reactor, preferred pressure autoclave type reactor, can carry out high pressure-temperature pre-treatment wherein thus.And the use of reactor is unrestricted, can to use in this area conventional tubular reactor, such as, vertical tubular reactor, as long as this reactor is suitable for collecting product liquid, and is suitable for catalyzer and raw material fully mixes.
Beneficial effect of the present invention:
1. method of the present invention opens one is produced the liquid fuels such as acetone, Virahol, butanone, butanols and ethanol new route by glucose catalytic pyrolysis.
2. method of the present invention is very short for reaction time, and production concentration is higher, is easy to separation and purification.
3. method choice of the present invention is high, and process is simple, is easy to control, and principal product is easy to be separated, and by-product liquid fuel, organism utilization rate is high, has very high economic worth and prospects for commercial application.
Embodiment
Further describe technical scheme of the present invention and effect by the following examples, it should be appreciated by those skilled in the art that following embodiment is only for illustration of the present invention, does not really want to limit the scope of the invention.
Embodiment 1
By 40g glucose and 20g calcium oxide, 50g water mixes, and is placed in pressure autoclave type reactor, in 170 DEG C, 10hr is reacted under 0.8MPa, the mixture obtained mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 500 DEG C, reaction 1hr, collect and be obtained by reacting liquid 10.2g, wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.61g, 2.41g, 0.52g, 2.00g and 0.18g.
Embodiment 2
By 40g glucose and 20g sodium hydroxide, 50g water mixes, and is placed in pressure autoclave type reactor, in 170 DEG C, 5hr is reacted under 0.8MPa, the mixture obtained mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 500 DEG C, reaction 1hr, collect and be obtained by reacting liquid 9.1g, wherein acetone, Virahol, butanone, butanols and ethanol are respectively 2.03g, 0.51g, 1.77g, 0.40g and 0.18g.
Embodiment 3
By 40g glucose and 10g calcium oxide, 10g sodium hydroxide, 50g water mixes, be placed in pressure autoclave type reactor, in 170 DEG C, 3hr is reacted under 0.8MPa, the mixture obtained mixes with 20g sodium hydroxide, be placed in tubular reactor, the gas mixture (throughput ratio is 1: 1) of logical nitrogen and water vapour is reaction atmosphere, is heated to 500 DEG C, reaction 1hr, collection is obtained by reacting liquid 1.3g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.22g, 0.07g, 0.23g, 0.08g and 0.03g.
Embodiment 4
By 40g glucose and 20g calcium oxide, 50g water mixes, be placed in pressure autoclave type reactor, in 170 DEG C, 3hr is reacted under 0.8MPa, the mixture obtained mixes with 20g calcium oxide, be placed in tubular reactor, the gas mixture (throughput ratio is 1: 1) of logical nitrogen and water vapour is reaction atmosphere, be heated to 500 DEG C, reaction 1hr, collect and be obtained by reacting liquid 11.0g, wherein acetone, Virahol, butanone, butanols and ethanol are respectively 2.47g, 0.63g, 2.05g, 0.51g and 0.20g.
Embodiment 5
By 40g glucose and 20g calcium oxide, 50g water mixes, and is placed in pressure autoclave type reactor, in 170 DEG C, 1hr is reacted under 0.8MPa, the mixture obtained mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 140 DEG C, reaction 2hr, collect and be obtained by reacting liquid 0.4g, wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.02g, 0.05g, 0.02g, 0.05g and 0.01g.
Embodiment 6
By 40g glucose and 10g calcium oxide, 10g sodium hydroxide, 50g water mixes, be placed in pressure autoclave type reactor, in 170 DEG C, 3hr is reacted under 0.8MPa, the mixture obtained mixes with 20g calcium oxide, be placed in tubular reactor, the gas mixture (throughput ratio is 1: 1) of logical nitrogen and water vapour is reaction atmosphere, is heated to 700 DEG C, reaction 2hr, collection is obtained by reacting liquid 11.8g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.66g, 2.48g, 0.58g, 2.59g and 0.21g.
Embodiment 7
By 40g glucose and 20g calcium oxide, 50g water mixes, and is placed in pressure autoclave type reactor, in 170 DEG C, 3hr is reacted under 0.8MPa, the mixture obtained mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 300 DEG C, reaction 0.1hr, collect and be obtained by reacting liquid 0.1g, wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.01g, 0.02g, 0.01g, 0.02g and trace.
Embodiment 8
By 40g glucose and 20g calcium oxide, 50g water mixes, and is placed in pressure autoclave type reactor, in 170 DEG C, 1hr is reacted under 0.8MPa, the mixture obtained mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 700 DEG C, reaction 0.1hr, collect and be obtained by reacting liquid 9.9g, wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.50g, 2.00g, 0.47g, 1.96g and 0.12g.
Embodiment 9
By 40g glucose and 20g calcium oxide, 50g water mixes, and is placed in pressure autoclave type reactor, in 100 DEG C, 3hr is reacted under 0.1MPa, the mixture obtained mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 500 DEG C, reaction 1hr, collect and be obtained by reacting liquid 1.0g, wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.05g, 0.20g, 0.04g, 0.16g and 0.01g.
Embodiment 10
By 40g glucose and 20g calcium oxide, 50g water mixes, and is placed in pressure autoclave type reactor, in 250 DEG C, 3hr is reacted under 4.0MPa, the mixture obtained mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 500 DEG C, reaction 1hr, collect and be obtained by reacting liquid 10.8g, wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.60g, 2.40g, 0.50g, 1.94g and 0.11g.
Claims (10)
1. utilize a method for Dextrose production liquid fuel, said method comprising the steps of: add tank reactor after being mixed with excessive basic catalyst by glucose, wherein excessive basic catalyst and the mol ratio of glucose are greater than 1; Pre-treatment is carried out under the pressure of the temperature of 100 DEG C ~ 250 DEG C and 0.1MPa ~ 4.0MPa, mixture pre-treatment obtained adds tubular reactor after mixing with excessive described basic catalyst further, and the mol ratio of the glucose in the mixture that wherein excessive described basic catalyst and pre-treatment obtain is greater than 1; Under the atmosphere of rare gas element, water vapour or both mixed gass and at the heating temperatures of 140 DEG C ~ 700 DEG C, react 0.1hr ~ 2hr, collect the product liquid be obtained by reacting, described product liquid comprises liquid fuel.
2. method according to claim 1, is characterized in that described basic catalyst is selected from the mixture of a kind of in the oxide compound of basic metal or alkaline-earth metal or oxyhydroxide or any two kinds.
3. method according to claim 2, is characterized in that described basic metal is sodium.
4. method according to claim 2, is characterized in that described alkaline-earth metal is calcium.
5. method according to claim 1, is characterized in that described basic catalyst is the mixture of calcium oxide and sodium hydroxide.
6. method according to claim 5, is characterized in that the mol ratio of calcium oxide and sodium hydroxide is 1:1 ~ 1:5.
7. the method according to any one of claim 1-6, is characterized in that the described pretreated time is 1hr ~ 10hr.
8. the method according to any one of claim 1-6, is characterized in that described rare gas element is nitrogen.
9. the method according to any one of claim 1-6, is characterized in that temperature of reaction is 300 DEG C ~ 700 DEG C.
10. the method according to any one of claim 1-6, is characterized in that described liquid fuel is the mixture of acetone, Virahol, butanols, butanone and ethanol.
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| CN103897716A CN103897716A (en) | 2014-07-02 |
| CN103897716B true CN103897716B (en) | 2016-03-16 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1668554A (en) * | 2002-05-10 | 2005-09-14 | 威斯康星旧生研究基金会 | Low-temperature hydrocarbon production from oxygenated hydrocarbons |
| WO2010025241A2 (en) * | 2008-08-27 | 2010-03-04 | Virent Energy Systems, Inc. | Synthesis of liquid fuels from biomass |
| CN102190562A (en) * | 2010-03-17 | 2011-09-21 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol from polyols |
| CA2792519A1 (en) * | 2010-03-18 | 2011-09-22 | Institut Technologique Fcba | Method for the depolymerisation of lignocellulosic biomass |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1668554A (en) * | 2002-05-10 | 2005-09-14 | 威斯康星旧生研究基金会 | Low-temperature hydrocarbon production from oxygenated hydrocarbons |
| WO2010025241A2 (en) * | 2008-08-27 | 2010-03-04 | Virent Energy Systems, Inc. | Synthesis of liquid fuels from biomass |
| CN102190562A (en) * | 2010-03-17 | 2011-09-21 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol from polyols |
| CA2792519A1 (en) * | 2010-03-18 | 2011-09-22 | Institut Technologique Fcba | Method for the depolymerisation of lignocellulosic biomass |
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