CN100999676A - Process of preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis - Google Patents
Process of preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis Download PDFInfo
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- CN100999676A CN100999676A CNA2006101560398A CN200610156039A CN100999676A CN 100999676 A CN100999676 A CN 100999676A CN A2006101560398 A CNA2006101560398 A CN A2006101560398A CN 200610156039 A CN200610156039 A CN 200610156039A CN 100999676 A CN100999676 A CN 100999676A
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Abstract
The microwave catalytic biomass cracking process for preparing biological oil with rich acetone alcohol features using sodium carbonate as catalyst, silicon carbide as microwave absorbing medium, microwave source as heat source for cracking biomass, and ice water mixture for cooling volatile component to obtain biological oil with rich acetone alcohol. By means of the unique temperature effect of microwave in biomass particle and the unique catalyzing effect of sodium carbonate in cracking biomass, the present invention realizes the creation of acetone alcohol in high selectivity. The present invention can obtain liquid product with acetone alcohol content of 30-55 % and raise the utilization value of acetone alcohol greatly. The present invention uses cheap and facile material and catalyst and has greatly shortened reaction period.
Description
Technical field
The present invention relates to a kind of preparation method of Organic Chemicals, promptly be rich in the method for acetone alcohol biological oil with the biomass preparation.
Background technology
The energy and environmental problem have become the focus that the whole world is paid close attention at present, and fossil fuel resource is still being played the part of the role of world energy sources pillar and large organic chemical industry's rule of origin.Fossil oil is when promoting the well-being of mankind, and also the environment of depending on for existence to the mankind has caused severe contamination, and fossil oil must exhaust in the near future, and it is imperative to seek its alternate resources.Biomass enlarge and optimize it and utilize the common recognition that has become the whole world as unique renewable energy source that can be converted into liquid fuel.Liquid fuel by biomass cracking is transformed is commonly referred to bio oil, is substantially free of sulphur, nitrogen and metal ingredient, environmentally safe.Except from the energy utilization angle is considered, also, can be used as the primary raw materials of many organic chemical industry's products because of containing the organism of abundant higher utility value in the bio oil.By the regulating effect of different catalysts, can realize that different organic highly selectivies generate.
The liquid product of biomass flash pyrolysis technology acquisition is at present formed complicated, is difficult to realize the highly selective generation of specific organic composition.Thereby fast there is the separation difficulty problem in the cracked liquid product as the application of Organic Chemicals.In order to enlarge the range of application of cracked oil, be necessary to improve technology, realize that the highly selective of specific organic constituent generates.
Hydroxyacetone is very important pharmaceutical-chemical intermediate, is used for the H of synthetic Digestive tract
2Intermediate (s)-(+)-2-aminopropanol of the intermediate 4-methylimidazole of blocade Cimitidine Type A/AB, Comprecin Levofloxacin, the intermediate 4-hydroxy methylimidazole of racemize Histidine, medicine and the chiral intermediates (1)-(-)-1 such as antipyretic and analgesic acetylsalicylic acid acetone ester that also are used for vitamin H (vitamin H) and do not have the ulcer toxic side effect, 2-propylene glycol synthetic.Synthetic or the production method of hydroxyacetone mainly contains: a martonite esterification/alcoholysis method and 1, the oxygen of 2-propylene glycol or K
2Cr
2O
7/ H
2SO
4Oxidation style etc.The former reaction conditions gentleness is the disadvantage of this method but the price of main raw material one martonite causes production cost too high; Latter reaction's condition and equipment requirements height, needs use expensive metal catalyst, product yield not high.
Though contain the hydroxyacetone component in the bio oil that the flash pyrolysis of biomass in fluidized bed technology obtains at present, content is lower, below 10%, utility value is low usually.
Summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology problem, a kind of method of preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis is provided, to overcome raw materials cost height in the prior art, catalyzer costliness, problem that hydroxyacetone content is low.
The technical scheme that technical solution problem of the present invention is adopted is:
With yellow soda ash is catalyzer, is the microwave absorbing medium with silicon carbide, is that heating source carries out biomass cracking with the microwave source, adopts frozen water miscellany cooling volatile matter to obtain to be rich in the bio oil of hydroxyacetone.
The characteristics of the inventive method also are:
The biomass material sawdust is removed free water as standby material through the aqueous sodium carbonate dipping after drying as catalyzer; Standby material and silicon carbide are by mass ratio 3: after 3-4 mixes, place the microwave field of 2450KHz to carry out cracking, collect volatile matter with nitrogen purging, split product obtains liquid product through the cooling of ice bath U type pipe.
Specifically operation according to the following procedure:
Biomass material sawdust median size is less than 1mm, in the aqueous sodium carbonate of 5% (w/w), flood half an hour, by weight percentage, the alkali lye consumption is the make a living 9-11% of material sawdust of institute's alkalinity, biomass sawdust behind the dipping dries earlier diel naturally, removes free water down in dry 3 hours as standby material at 105 ℃ again; Is 3 with silicon carbide by mass ratio with standby material: 3-4 mixes charging, places the microwave cracking reactor to carry out cracking, microwave initial power 1kw, and adjusting microwave power when temperature reaches 470 ℃ is 0.3kw, and holding temperature is 450-550 ℃, and cracking pressure is normal pressure; Nitrogen flow is 0.15-0.25m3/h, and split product acquires the bio oil that is rich in hydroxyacetone through multistage ice bath " U " the shape pipe that series connection is provided with successively.
Standby material mixes charging with silicon carbide be to replace bedding in quartz reactor, and every layer of shop 0.5-1mm spreads the 14-18 layer altogether.
Compared with the prior art, the profitable fruit of the present invention is embodied in:
1, the present invention utilizes unique temperature effective that microwave forms in biomass particle, and yellow soda ash in microwave field to unique catalytic effect of biomass cracking, realized that the highly selective of hydroxyacetone generates.Can reach 30-55% by the content of hydroxyacetone in product liquid that present method obtained, compare below 10% to have very with the hydroxyacetone content in the quick cracking bio oil of present fluidized-bed and increase substantially, the utility value of hydroxyacetone is higher.
2, the raw material and the catalyzer of the inventive method use are cheap and easy to get, and the reaction times shortens greatly.
Description of drawings
Accompanying drawing is the inventive method schematic flow sheet.
Number in the figure: 1 nitrogengas cylinder, 2 quartz reactors, 3 one-level U-shaped pipes, 4 secondary U-shaped pipes, 5 three grades of U-shaped pipes, 6 ice-water baths, 7 microwave cavities.
Below pass through embodiment, and the invention will be further described in conjunction with the accompanying drawings:
Embodiment
Concrete enforcement is carried out as follows:
1, feedstock production
With the biomass material sawdust be median size less than 1mm, in the aqueous sodium carbonate of 5% (w/w), flood, the alkali lye consumption should make the make a living 9-11% of material sawdust quality of institute's alkalinity wherein.Dry diel after fully stirring, again in baking oven 105 ℃ dry 3 hours down, remove free water and be placed on moisture eliminator as standby material.
2, charging
Take by weighing the 16.5g standby material, mix charging with 20g silicon carbide, concrete operations are alternating thin layers beddings in quartz reactor 2 with standby material and silicon carbide, spread the 14-18 layer altogether, every layer of 0.5-1mm.Cover the ground reactor cap, quartz reactor 2 is placed microwave cavity 7, connect gas introduction tube that is communicated with nitrogengas cylinder 1 and the gas eduction tube that is communicated with one-level U-shaped pipe 3.
3, emptying gas
Open nitrogengas cylinder 1, keep flow 0.15-0.2m
3/ h, aeration time at least 10 minutes is discharged the air in quartz reactor 2 and the piping system.
4, microwave cracking
Open microwave (2450KHz), about initial power 1kw, the reaction mass temperature reaches 470 ℃, turns down power to 0.3kw, keeps temperature of charge.Treat liquid distillate finish after, close microwave, stop cracking.Collection places the liquid of one-level U-shaped pipe 3, secondary U-shaped pipe 4 and three grades of U-shaped pipes 5 of ice-water bath 6 promptly to get the mixing organic liquid that is rich in hydroxyacetone, the liquid product yield is between 10～25%, wherein moisture 20～30%, the content 30-55% of hydroxyacetone in organic liquid.General liquid begins to distillate after microwave is opened 3 minutes, no longer includes tangible liquid overhead product after 8 minutes.
Embodiment 1:
With the pine tree sawdust is raw material, and it is crushed to particle diameter is below the 1mm, carries out feedstock production, charging, emptying gas and microwave cracking with the inventive method, and the cracking time is 12 minutes, collects product liquid.The yield of product liquid is 22.0%, and hydroxyacetone content is 45.3%, and water ratio is 28.2%.
Embodiment 2:
With the cotton stalk sawdust is raw material, adopts step similarly to Example 1, collects product liquid.The yield of product liquid is 15.8%, and hydroxyacetone content is 49.9%, and water ratio is 30.3%.
Embodiment 3:
With the China fir sawdust is raw material, adopts step similarly to Example 1, collects product liquid.The yield of product liquid is 24.7%, and hydroxyacetone content is 45.4%, and water ratio is 29.6%.
Claims (4)
1, the method for preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis, it is characterized in that with yellow soda ash being catalyzer, with silicon carbide is the microwave absorbing medium, is that heating source carries out biomass cracking with the microwave source, adopts frozen water miscellany cooling volatile matter to obtain to be rich in the bio oil of hydroxyacetone.
2, the method for preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis according to claim 1 is characterized in that the biomass material sawdust floods after drying through the aqueous sodium carbonate as catalyzer and removes free water as standby material; Standby material and silicon carbide are by mass ratio 3: after 3-4 mixes, place the microwave field of 2450KHz to carry out cracking, collect volatile matter with nitrogen purging, split product obtains liquid product through the cooling of ice bath U type pipe.
3, the method for preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis according to claim 1 is characterized in that operating according to the following procedure:
Biomass material sawdust median size is less than 1mm, in 5% aqueous sodium carbonate, flood half an hour, by weight percentage, the alkali lye consumption is the make a living 9-11% of material sawdust of institute's alkalinity, biomass sawdust behind the dipping dries earlier diel naturally, removes free water down in dry 3 hours as standby material at 105 ℃ again; Is 3 with silicon carbide by mass ratio with standby material: 3-4 mixes charging, places the microwave cracking reactor to carry out cracking, microwave initial power 1kw, and adjusting microwave power when temperature reaches 470 ℃ is 0.3kw, and holding temperature is 450-550 ℃, and cracking pressure is normal pressure; Nitrogen flow is 0.15-0.25m3/h, and split product acquires the bio oil that is rich in hydroxyacetone through multistage ice bath " U " the shape pipe that series connection is provided with successively.
4, the method for preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis according to claim 3 is characterized in that standby material mixes charging with silicon carbide be to replace bedding in quartz reactor, and every layer of shop 0.5-1mm spreads the 14-18 layer altogether.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235312B (en) * | 2008-02-29 | 2011-05-04 | 上海大学 | Method for preparing biological oil by using microwave irradiation to crack biomass |
| CN102199440A (en) * | 2011-04-20 | 2011-09-28 | 安徽理工大学 | Method for preparing low-acidity and low-oxygen content biological oil by two-section conversion |
| CN101684069B (en) * | 2008-09-24 | 2012-09-26 | 中国科学院过程工程研究所 | Method for enriching acetol from biomass pyrolysis liquid aqueous phase system |
| WO2014041373A2 (en) | 2012-09-16 | 2014-03-20 | Hall Philip Lawrence Timothy Richard | Apparatus and method for processing municipal waste into bio-ethanol |
| CN104818038A (en) * | 2015-05-18 | 2015-08-05 | 南京农业大学 | Biomass microwave cracking system |
| CN106635110A (en) * | 2016-10-27 | 2017-05-10 | 陕西科技大学 | Method for preparing liquid product containing rich phenols and alcohols through microwave catalytic thermal cracking of forestry and agricultural residues |
| CN106674458A (en) * | 2016-12-26 | 2017-05-17 | 陕西科技大学 | Method for preparing environment-friendly resin from microwave thermally-cracked liquid products of forestry wastes |
| WO2020088172A1 (en) * | 2018-10-29 | 2020-05-07 | 中国石油化工股份有限公司 | Continuous operation method for microwave high-temperature pyrolysis of solid material comprising organic matter |
| CN111618076A (en) * | 2020-06-17 | 2020-09-04 | 中国科学院合肥物质科学研究院 | Industrial waste salt treatment system based on microwave pyrolysis method |
| CN112010824A (en) * | 2020-08-21 | 2020-12-01 | 中国科学院广州能源研究所 | Method for selectively preparing high-value product by fast pyrolysis of cassava residue |
Family Cites Families (3)
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| US4678860A (en) * | 1985-10-04 | 1987-07-07 | Arizona Board Of Regents | Process of producing liquid hydrocarbon fuels from biomass |
| CN100365099C (en) * | 2006-02-27 | 2008-01-30 | 淮北市辉克药业有限公司 | Novel technology for producing liquid fuel using biomass |
| CN100417708C (en) * | 2006-06-02 | 2008-09-10 | 大连理工大学 | Method for preparing biodiesel from sludge by microwave radiation |
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2006
- 2006-12-31 CN CN2006101560398A patent/CN100999676B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235312B (en) * | 2008-02-29 | 2011-05-04 | 上海大学 | Method for preparing biological oil by using microwave irradiation to crack biomass |
| CN101684069B (en) * | 2008-09-24 | 2012-09-26 | 中国科学院过程工程研究所 | Method for enriching acetol from biomass pyrolysis liquid aqueous phase system |
| CN102199440A (en) * | 2011-04-20 | 2011-09-28 | 安徽理工大学 | Method for preparing low-acidity and low-oxygen content biological oil by two-section conversion |
| WO2014041373A2 (en) | 2012-09-16 | 2014-03-20 | Hall Philip Lawrence Timothy Richard | Apparatus and method for processing municipal waste into bio-ethanol |
| CN104818038A (en) * | 2015-05-18 | 2015-08-05 | 南京农业大学 | Biomass microwave cracking system |
| CN106635110B (en) * | 2016-10-27 | 2018-04-06 | 陕西科技大学 | A kind of agriculture and forestry organic waste material microwave catalysis thermal cracking is prepared rich in phenols, the method for alcohol-based liquid product |
| CN106635110A (en) * | 2016-10-27 | 2017-05-10 | 陕西科技大学 | Method for preparing liquid product containing rich phenols and alcohols through microwave catalytic thermal cracking of forestry and agricultural residues |
| CN106674458A (en) * | 2016-12-26 | 2017-05-17 | 陕西科技大学 | Method for preparing environment-friendly resin from microwave thermally-cracked liquid products of forestry wastes |
| CN106674458B (en) * | 2016-12-26 | 2018-10-09 | 陕西科技大学 | A kind of method that forestry waste microwave thermal cracking product liquid prepares environmental protection type resin |
| WO2020088172A1 (en) * | 2018-10-29 | 2020-05-07 | 中国石油化工股份有限公司 | Continuous operation method for microwave high-temperature pyrolysis of solid material comprising organic matter |
| US11926794B2 (en) | 2018-10-29 | 2024-03-12 | China Petroleum & Chemical Corporation | Continuous operation method for microwave high-temperature pyrolysis of solid material comprising organic matter |
| CN111618076A (en) * | 2020-06-17 | 2020-09-04 | 中国科学院合肥物质科学研究院 | Industrial waste salt treatment system based on microwave pyrolysis method |
| CN112010824A (en) * | 2020-08-21 | 2020-12-01 | 中国科学院广州能源研究所 | Method for selectively preparing high-value product by fast pyrolysis of cassava residue |
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| CN100999676B (en) | 2011-06-08 |
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