CN103897717A - Method used for preparing liquid fuel from cellulose - Google Patents
Method used for preparing liquid fuel from cellulose Download PDFInfo
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- CN103897717A CN103897717A CN201210571350.4A CN201210571350A CN103897717A CN 103897717 A CN103897717 A CN 103897717A CN 201210571350 A CN201210571350 A CN 201210571350A CN 103897717 A CN103897717 A CN 103897717A
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- liquid fuel
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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
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- 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 invention relates to a method used for preparing liquid fuel from cellulose. According to the method, cellulose is subjected to high pressure pretreatment under alkaline conditions, and an obtained mixed material is subjected to catalytic pyrolysis under alkaline conditions so as to obtain a mixture of liquid fuel acetone, isopropanol, butanol, butanone, and ethanol. The method is high in selectivity; processes are simple, and are easy to control; principal products are easy for separation; byproduct liquid fuel is obtained; utilization ratio of organic substances is high; economic value is high; and industrial application prospect is promising.
Description
Technical field
The invention belongs to a kind of novel method of utilizing Mierocrystalline cellulose preparing liquid fuel, the method is applicable to utilizing Mierocrystalline cellulose base catalysis cracking liquid fuel.
Background technology
Acetone, Virahol, butanone, butanols and ethanol are all important organic solvent and industrial chemicals, in the industry such as explosive, plastics, pharmacy and synthetic glass, synthetic rubber, are widely used.Acetone is important organic synthesis raw material, for the production of epoxy resin, and polycarbonate, synthetic glass etc., are also good solvents, also as thinner, clean-out system, extraction agent.Virahol is important Chemicals and raw material, for pharmacy, makeup, plastics, spices, coating etc.Butanone is mainly 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 also, 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.
To the early 1990s in last century, the synchronous production of acetone, butanols and ethanol is mainly to utilize grain fermentative production, from the nineties, is replaced by petrochemical complex method.Now day by day serious along with the day by day exhausted and environmental problem of petroleum resources, adopts new method production acetone, butanols and ethanol to cause the extensive concern of countries in the world.
Chinese patent CN101161818A has proposed a kind of method that adopts B-Starch from Wheat replacement of corn fermentation production of acetone-butanol.Chinese patent CN101363031 has proposed take maize peel as raw material, carries out the production method of acetone-butanol through processes such as steaming and decocting under high pressure, enzymatic saccharifications.Chinese patent CN101358218A has proposed a kind of method of 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 has proposed a kind of take xylose production waste liquid as raw material, utilizes microbial fermentation technology bio-transformation sugar source production chemical product acetone-butanol.Chinese patent CN102286549A has proposed a kind of method with cellobiose, xylose and glucose mixing sugar fermentation production of acetone-butanol.Chinese patent CN102304550A has proposed a kind of method take lignocellulose as raw material production ethanol or acetone-butanol, adopting wet dish shredder-ultra micron to melt broken machine physical method carries out lignocellulose after pre-treatment, to carry out fermentative production of ethanol or acetone-butanol.
Above-mentioned method is all take biofermentation technique as basis, 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, and the cycle of raw materials pretreatment is also all longer, does not utilize the production of bulk chemical.
Therefore the novel method that needs to research and develop the waste liquid fuel that a kind of utilization is easy to get, the reaction time of the method should be shorter, and production concentration is higher and 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 of utilizing Mierocrystalline cellulose preparing liquid fuel, the method is short reaction time, and production concentration is higher, and is easy to separation and purification.
Therefore, the invention provides a kind of method (below sometimes referred to as " method of the present invention ") of utilizing Mierocrystalline cellulose preparing liquid fuel, said method comprising the steps of: by cellulosic material and excessive basic catalyst (, basic catalyst is greater than 1 with the mol ratio of cellulosic material) add tank reactor after mixing, under the pressure of the temperature of 100 ℃-250 ℃ and 0.1MPa-4.0MPa, carry out pre-treatment, the mixture that pre-treatment is obtained and excessive basic catalyst are (, basic catalyst is greater than 1 with the mol ratio of cellulosic material in mixture) add tubular reactor after mixing, at rare gas element, under the atmosphere of water vapour or both mixed gass and at 140 ℃～700 ℃, the temperature reacting by heating 0.1hr～2hr of preferably 300 ℃～700 ℃, preferably 1h～2h, collect the product liquid that reaction obtains, described product liquid comprises liquid fuel.
In the method for the invention, cellulosic material and basic catalyst all can add with the form of solid, for example, directly with commercially available raw material form, or after suitable pulverizing or grinding plant processing, make powder or particle form interpolation.If with powder or particle form charging, 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, the mixture that is calcium oxide and sodium hydroxide at basic catalyst, 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 the mixed gas (both ratios are unrestricted, for example, can adopt the throughput ratio of 1: 1) of nitrogen or nitrogen and water vapour.
In the method for the invention, the liquid fuel comprising in product liquid can be the mixture of the products such as acetone, Virahol, butanone, butanols and ethanol, and content ratio and the distribution meeting separately of every kind of liquid fuel changes according to the difference of operational condition.
In the present invention, pretreated reactor can adopt tank reactor, and preferably high pressure tank reactor, can carry out high pressure-temperature pre-treatment thus therein.And the use of reactor is unrestricted, can use tubular reactor conventional in this area, for example, 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 has been opened up a new route of being produced the liquid fuels such as acetone, Virahol, butanone, butanols and ethanol by Mierocrystalline cellulose catalytic pyrolysis.
2. method selectivity of the present invention is high, and process is simple, is easy to control, and principal product is easy to separate, and by-product liquid fuel, and organism utilization ratio is high, has very high economic worth and prospects for commercial application.
3. in product liquid of the present invention, acetone, Virahol, butanone and butanols are main product, have ethanol to produce simultaneously, and the selectivity of acetone, Virahol, butanone and butanols is very high.
Embodiment
Further describe by the following examples technical scheme of the present invention and effect, it should be appreciated by those skilled in the art that following embodiment, only for the present invention is described, does not really want to limit the scope of the invention.
Embodiment 1
By 50g Mierocrystalline cellulose and 20g calcium oxide, 50g water mixes, and is placed in high pressure tank reactor, in 170 ℃, under 0.8MPa, react 3hr, the mixture obtaining mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 500 ℃, reaction 1hr, collects reaction and obtains liquid 10.7g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.59g, 2.44g, 0.50g, 2.02g and 0.17g.
Embodiment 2
By 50g Mierocrystalline cellulose and 20g sodium hydroxide, 50g water mixes, be placed in high pressure tank reactor, in 170 ℃, under 0.8MPa, react 3hr, the mixture obtaining 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 ℃, reaction 1hr, collects reaction and obtains liquid 9.3g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 2.00g, 0.52g, 1.71g, 0.42g and 0.16g.
Embodiment 3
By 50g Mierocrystalline cellulose and 20g calcium oxide, 50g water mixes, be placed in high pressure tank reactor, in 170 ℃, under 0.8MPa, react 3hr, the mixture obtaining 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, be heated to 500 ℃, reaction 1hr, collects reaction and obtains liquid 1.5g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.27g, 0.08g, 0.25g, 0.09g and 0.04g.
Embodiment 4
By 50g Mierocrystalline cellulose and 20g calcium oxide, 50g water mixes, and is placed in high pressure tank reactor, in 170 ℃, under 0.8MPa, react 3hr, the mixture obtaining mixes with 20g calcium oxide, is placed in tubular reactor, and water flowing steam is reaction atmosphere, be heated to 500 ℃, reaction 1hr, collects reaction and obtains liquid 11.0g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 2.47g, 0.66g, 2.07g, 0.57g and 0.20g.
Embodiment 5
By 50g Mierocrystalline cellulose and 20g calcium oxide, 50g water mixes, and is placed in high pressure tank reactor, in 170 ℃, under 0.8MPa, react 3hr, the mixture obtaining mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 140 ℃, reaction 2hr, collects reaction and obtains liquid 0.4g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.02g, 0.05g, 0.02g, 0.05g and 0.01g.
Embodiment 6
By 50g Mierocrystalline cellulose and 20g sodium hydroxide, 50g water mixes, and is placed in high pressure tank reactor, in 170 ℃, under 0.8MPa, react 3hr, the mixture obtaining mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 700 ℃, reaction 2hr, collects reaction and obtains liquid 12.1g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.67g, 2.49g, 0.57g, 2.59g and 0.25g.
Embodiment 7
By 50g Mierocrystalline cellulose and 20g calcium oxide, 50g water mixes, and is placed in high pressure tank reactor, in 170 ℃, under 0.8MPa, react 3hr, the mixture obtaining mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 200 ℃, reaction 0.1hr, collects reaction and obtains liquid 0.1g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.01g, 0.02g, 0.01g, 0.02g and trace.
Embodiment 8
By 50g Mierocrystalline cellulose and 20g calcium oxide, 50g water mixes, and is placed in high pressure tank reactor, in 170 ℃, under 0.8MPa, react 3hr, the mixture obtaining mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 700 ℃, reaction 0.1hr, collects reaction and obtains liquid 9.0g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.51g, 2.00g, 0.47g, 1.94g and 0.13g.
Embodiment 9
By 50g Mierocrystalline cellulose and 20g calcium oxide, 50g water mixes, and is placed in high pressure tank reactor, in 100 ℃, under 0.1MPa, react 3hr, the mixture obtaining mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 300 ℃, reaction 1hr, collects reaction and obtains liquid 1.2g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.06g, 0.20g, 0.05g, 0.20g and 0.01g.
Embodiment 10
By 50g Mierocrystalline cellulose and 20g calcium oxide, 50g water mixes, and is placed in high pressure tank reactor, in 250 ℃, under 4.0MPa, react 3hr, the mixture obtaining mixes with 20g calcium oxide, is placed in tubular reactor, and logical nitrogen is reaction atmosphere, be heated to 500 ℃, reaction 1hr, collects reaction and obtains liquid 13.4g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.60g, 1.80g, 0.50g, 1.71g and 0.11g.
Embodiment 11
By 50g Mierocrystalline cellulose and 20g calcium oxide, 20g sodium hydroxide, 50g water mixes, be placed in high pressure tank reactor, in 100 ℃, under 0.1MPa, react 1hr, the mixture obtaining mixes with 20g calcium oxide, be placed in tubular reactor, logical nitrogen is reaction atmosphere, is heated to 300 ℃, reaction 1hr, collect reaction and obtain liquid 1.2g, wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.05g, 0.21g, 0.07g, 0.22g and 0.02g.
Embodiment 12
By 50g Mierocrystalline cellulose and 20g calcium oxide, 20g sodium hydroxide, 50g water mixes, be placed in high pressure tank reactor, in 250 ℃, under 0.1MPa, react 10hr, the mixture obtaining mixes with 20g calcium oxide, be placed in tubular reactor, logical nitrogen is reaction atmosphere, is heated to 300 ℃, reaction 1hr, collect reaction and obtain liquid 12.7g, wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.79g, 2.67g, 0.53g, 2.32g and 0.19g.
Claims (10)
1. one kind is utilized the method for Mierocrystalline cellulose preparing liquid fuel, said method comprising the steps of: after Mierocrystalline cellulose is mixed with excessive basic catalyst, add tank reactor, under the pressure of the temperature of 100 ℃-250 ℃ and 0.1MPa-4.0MPa, carry out pre-treatment, the mixture that pre-treatment is obtained adds tubular reactor after further mixing with excessive described basic catalyst, at rare gas element, under the atmosphere of water vapour or both mixed gass and at the temperature reacting by heating 0.1hr～2hr of 140 ℃-700 ℃, collect the product liquid that reaction obtains, 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. according to the method in claim 2 or 3, it 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, the mol ratio that it is characterized in that calcium oxide and sodium hydroxide is 1: 1～1: 5.
7. according to the method described in any one in claim 1-6, it is characterized in that the described pretreated time is 1hr～10hr.
8. according to the method described in any one in claim 1-7, it is characterized in that described rare gas element is nitrogen.
9. according to the method described in any one in claim 1-8, it is characterized in that temperature of reaction is 300 ℃～700 ℃.
10. according to the method described in any one in claim 1-9, it is characterized in that described liquid fuel is the mixture of acetone, Virahol, butanols, butanone and ethanol.
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| CN201210571350.4A CN103897717B (en) | 2012-12-25 | 2012-12-25 | A kind of method utilizing Mierocrystalline cellulose preparing liquid fuel |
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| CN201210571350.4A CN103897717B (en) | 2012-12-25 | 2012-12-25 | A kind of method utilizing Mierocrystalline cellulose preparing liquid fuel |
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| CN103897717A true CN103897717A (en) | 2014-07-02 |
| CN103897717B CN103897717B (en) | 2016-02-10 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234887A (en) * | 2020-02-11 | 2020-06-05 | 东南大学 | Preparation method of long-chain oxygen-containing liquid fuel precursor |
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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234887A (en) * | 2020-02-11 | 2020-06-05 | 东南大学 | Preparation method of long-chain oxygen-containing liquid fuel precursor |
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