CN103897717B - A kind of method utilizing Mierocrystalline cellulose preparing liquid fuel - Google Patents
A kind of method utilizing Mierocrystalline cellulose preparing liquid fuel Download PDFInfo
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- CN103897717B CN103897717B CN201210571350.4A CN201210571350A CN103897717B CN 103897717 B CN103897717 B CN 103897717B CN 201210571350 A CN201210571350 A CN 201210571350A CN 103897717 B CN103897717 B CN 103897717B
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- 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 Mierocrystalline cellulose preparing liquid fuel.Method of the present invention utilizes Mierocrystalline cellulose 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 Mierocrystalline cellulose preparing liquid fuel, the method is applicable to utilizing cellulose alkaline catalytic pyrolysis to produce 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.It take lignocellulose as the method for raw material production ethanol or acetone-butanol that Chinese patent CN102304550A proposes a kind of, adopt wet dish shredder-ultra micron to melt after lignocellulose carries out pre-treatment by broken machine physical method, carry out fermentative production of ethanol or 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, and the cycle of raw materials pretreatment is also all longer, does not utilize the production of bulk chemical.
Therefore need the novel method researching and developing 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 utilizing Mierocrystalline cellulose preparing 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 Mierocrystalline cellulose preparing liquid fuel (below sometimes referred to as " method of the present invention "), said method comprising the steps of: by cellulosic material and excessive basic catalyst (namely, basic catalyst is greater than 1 with the mol ratio of cellulosic material) 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 cellulosic material 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, cellulosic material 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 the mixed gas (both ratios are unrestricted, such as, can adopt the throughput ratio of 1: 1) of nitrogen or nitrogen and water vapour.
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 a new route by liquid fuels such as cellulose catalytic cracking acetone, Virahol, butanone, butanols and ethanol.
2. 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.
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 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 50g Mierocrystalline cellulose 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 500 DEG C, reaction 1hr, collect and be obtained by reacting liquid 10.7g, 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 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 9.3g, 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 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, be heated to 500 DEG C, reaction 1hr, collect and be obtained by reacting liquid 1.5g, 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 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 water flowing steam 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, 0.66g, 2.07g, 0.57g and 0.20g.
Embodiment 5
By 50g Mierocrystalline cellulose and 20g calcium oxide, 50g water mixes, and is placed in 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 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 50g Mierocrystalline cellulose and 20g sodium hydroxide, 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 700 DEG C, reaction 2hr, collect and be obtained by reacting liquid 12.1g, 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 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 200 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 50g Mierocrystalline cellulose 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 700 DEG C, reaction 0.1hr, collect and be obtained by reacting liquid 9.0g, 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 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 300 DEG C, reaction 1hr, collect and be obtained by reacting liquid 1.2g, 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 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 13.4g, 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 pressure autoclave type reactor, in 100 DEG C, react 1hr under 0.1MPa, the mixture obtained mixes with 20g calcium oxide, be placed in tubular reactor, logical nitrogen is reaction atmosphere, is heated to 300 DEG C, reaction 1hr, collection is obtained by reacting liquid 1.2g, and 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 pressure autoclave type reactor, in 250 DEG C, react 10hr under 0.1MPa, the mixture obtained mixes with 20g calcium oxide, be placed in tubular reactor, logical nitrogen is reaction atmosphere, is heated to 300 DEG C, reaction 1hr, collection is obtained by reacting liquid 12.7g, and wherein acetone, Virahol, butanone, butanols and ethanol are respectively 0.79g, 2.67g, 0.53g, 2.32g and 0.19g.
Claims (10)
1. utilize a method for Mierocrystalline cellulose preparing liquid fuel, said method comprising the steps of: add tank reactor after being mixed with excessive basic catalyst by Mierocrystalline cellulose, wherein excessive basic catalyst and cellulosic mol ratio 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 cellulosic mol ratio 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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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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| 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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