CN101811131B - Method for comprehensively utilizing biomass waste containing rich silicon - Google Patents
Method for comprehensively utilizing biomass waste containing rich silicon Download PDFInfo
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- CN101811131B CN101811131B CN2010101162503A CN201010116250A CN101811131B CN 101811131 B CN101811131 B CN 101811131B CN 2010101162503 A CN2010101162503 A CN 2010101162503A CN 201010116250 A CN201010116250 A CN 201010116250A CN 101811131 B CN101811131 B CN 101811131B
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Abstract
A method for comprehensively utilizing biomass waste containing rich silicon comprises the following steps that: firstly, agriculture and forestry biomass waste is extracted by using dichloromethane-ethanol and hot water to obtain bioactive materials with different uses, the balance is polymer cellulose, lignin and minerals, then the balance and polymer waste are cracked together, the lysate is hydrocarbon gas, oil-like hydrocarbons and oxygenated organic compound, and the residue is cracked to obtain silicide. Conversion percent of waste in the total mixed reaches 85-95%, hydrocarbon gas of the total product accounts for 15-22%, liquid hydrocarbons accounts for 38-56%, organic oxygen accounts for 19-25%, and the silicide accounts for 10-15%.
Description
Technical field
The present invention relates to a kind of technology that the biomass castoff that is rich in silicon is fully utilized, the biomass castoff that is specially to be rich in silicon prepares biological active matter, lysate and silicide through extracting cracking technique again.
Background technology
Reduce gradually at fossil resources such as oil, we face and use and disuse the dilemma that grain, feed come the conversion of biomass energy; Simultaneously, the annual agriculture and forestry organic waste material that increases is also perplexing our environmental protection; The researcher turns one's attention to agriculture and forestry organic waste material cleaning, efficient trans-utilization.The main composition of agriculture and forestry organic waste material is cellulose family, lignin, biological active matter and silicon class etc., as rice husk kind and place of production difference, it forms difference to some extent, roughly consists of: crude fibre 35.5%～45% (polycondensation pentose 16%～22%), wooden rope 21%～26%, silica 1 0%～21%.Contain multiple natural products in the leaf of bamboo, have effects such as good Green Tea Extract, anti-oxidant, anti-ageing, antibacterial bacteriostatic, desinsection, silicon also is rich in organizing of bamboo.In the nature soil constituent, oxygen accounts for 49%, and silicon accounts for 31%, and silicon is the second largest element that content is only second to oxygen in the earth's crust.Si oxide has constituted 50%～70% of soil material, so all are taken root all contain silicon in the plant tissue of soil.Silicon is difficult for moving in plant, so more silicon accumulates in old tissue.The content distribution scope of silicon in the plant dry weight is 0.1%～10.0%, and content has difference in different plant species.
The process of agriculture and forestry organic waste material living beings utilization is in the past all isolated, extracted active material from agriculture and forestry organic waste material after, remaining a large amount of slag is discarded, stacks contaminated environment nowhere; Current trend is directly handled biomass cracking, and the active matter of high value is not made full use of, burn in vain, and ash content or the mineral matter of remaining 10-20% of while, not handling also to become secondary pollution; Obtain the enterprise of silicide from living beings, directly obtain silicide behind the high temperature, pollute air, the waste resource; And do not consider the segmentation temperature raising, other series of products such as lysate can get both.
Summary of the invention
The object of the invention is efficient trans-utilization agriculture and forestry organic waste material, solves environmental protection and resource and energy shortage problem.A kind of technology that the biomass castoff that is rich in silicon is fully utilized is provided, can obtains multiple products such as biological active matter, lysate and silicide.
Provided by the invention to being rich in the biomass castoff comprehensive utilization method of silicon, at first to agricultural-forestry biomass discarded object carrene-pure and mild hot-water extraction, obtain the biological active matter of different purposes, remaining thing is high molecular cellulose and lignin, and mineral matter, through catalyst treatment, in normal pressure reactor, obtain lysate by the copyrolysis reaction with the polymer discarded object, the residue of cracking reaction remainder obtains silicide through handling, and preparation process is as follows:
1), will be rich in the biomass castoff of silicon, comprise rice husk, rice bar, bamboo class, wheat straw agricultural processing waste, it is dry to go foreign matter to pulverize, by dried biomass: carrene-pure weight ratio is 1: 10～20 extractings, use dried biomass again: the hot water weight ratio is 1: 5～15 extractings, extract concentrates, the recrement after acquisition biological active matter and the extracting;
2), with the polymer discarded object, comprise polystyrene, polyethylene, polypropylene, damaged tire and daily waste plastic, it is dry to go foreign matter to pulverize, recrement after the extracting in the step 1) is dried naturally, add catalyst inorganic acid or inorganic base by 0.3～3% of dry recrement raw material weight, recrement by drying: polymer weight ratio is 3～1: 1 mixing, enters in the reactor by feeder; Discharge the air in the reactor, the vacuum anaerobic under normal pressure, is warming up to 400～550 ℃ and carries out cracking reaction;
3), cracking limit, limit collects gaseous product, the hydrocarbon gas that contains C1～C4 obtains liquefiable gas through cryogenic condensation; The gas of not liquefiable imports the combustion chamber and provides energy for copyrolysis;
4), product liquid is collected, product liquid process layering acquisition hydrocarbon liquids product and water soluble organic substance in cracking limit, limit; Water soluble organic substance obtains different oxygen-bearing organic matters through after the upgrading;
5), the cracking reaction time is 0.5～3 hour, after reaction finishes, with the residue of cracking reaction remainder, is heated to 650 degree in quartz reactor, reacts 2 hours, obtains the canescence silicide.
The kind of mixed waste of the present invention: living beings comprise that rice husk, rice bar, bamboo class, wheat straw etc. are rich in silicon agricultural processing waste; The polymer discarded object comprises polystyrene (PS), polyethylene (PE), polypropylene (PP), damaged tire and daily waste plastic etc.
Agriculture and forestry organic waste material of the present invention removes foreign matter, and the polymer discarded object is ground into the particle that is less than 5mm.
Catalyst promoter of the present invention is inorganic acid, inorganic base; Consumption is 0.3～3% of a dry recrement raw material weight; Be preferably 2%.
Reaction condition of the present invention is: carry out the vacuum anaerobic under the normal pressure.Pyrolysis temperature is preferably 450～520 ℃ at 400～550 ℃.
In 0.5～3 hour reaction time of the present invention, be preferably 1～2.5 hour.
The present invention obtains biological active matter, lysate and silicide.With the solvent extraction two big class biological active matters of carrene-two kinds of opposed polarities of pure and mild hot water, biological active matter can further be processed different natural activity things.Lysate is gas hydro carbons, oily hydro carbons, oxygen-bearing organic matter.Silicide is for containing silica product.
The conversion ratio of the total mixed waste of the present invention reaches 85～95%, hydrocarbon-containifirst gas comprises 15～22% in the output aggregate, hydrocarbon compound liquid 38～56%, oxygen-bearing organic matter 19～25%, silicide 10～15%.
Compare with existing pyrolytic technique, agricultural-forestry biomass discarded object of the present invention obtains the organic matter of different purposes with carrene-pure and mild hot-water extraction, and the active matter of agricultural-forestry biomass discarded object high value is fully used; Make full use of the recrement of cracking after the pyrolysis again.The effect that stores and provide living radical has been played in the cracking of cellulose elder generation during the common pyrolysis of the present invention in reaction, represents that with simple formula its mechanism is: living beings → solid+free radical → free radical+polymer → chain rupture → light liquid phase product.The living beings process is converted into useful products to the environmental friendliness of waste of polymeric potential effect.The waste polymerizing thing as polyethylene and polypropylene, has comprised about 14% hydrogen.These materials can provide hydrogen with the common pyrolysis of living beings the time, and product liquid is increased.Hemicellulose at first decomposes between 200-260 ℃, produces volatile products; Cellulose decomposes between 260-350 ℃, and major part also is volatile products; The 3rd stage is the pyrolysis phase of lignin, and promptly 350-500 ℃, lignin slowly decomposed in this stage, finally generated carbon and ash content.Studies show that from the charcoal that living beings obtain, two effects are arranged: charcoal can be so that the temperature of polymer pyrolysis reduces and needed monomer of polymer cracking and dimer is provided.
Characteristics of the present invention: the technology of silicon biomass castoff comprehensive utilization is rich in (1) utilization of the present invention, efficient trans-utilization agriculture and forestry organic waste material, and solve environmental protection and resource and energy shortage problem.(2) the present invention utilizes extraction technique, copyrolysis technology, the integrated technology of silicon generation technique, concerted catalysis technology.(3) obtain biological active matter, lysate and silicide multiple product.(4) whole process is carried out in normal pressure, and equipment requires low, the working condition gentleness; Make full use of resource, avoided three waste discharge greatly, belonged to the environmental friendliness technology.
The specific embodiment
Embodiment 1
The 1st step: biomass castoff is removed foreign matter, pulverize dryly, by dried biomass: carrene-pure weight ratio is 1: 10～20 extractings, uses living beings again: 1: 5～15 extractings of hot water weight ratio, and extract is concentrated, obtains biological active matter and recrement 1;
The 2nd step: recrement 1 dries naturally, needs through catalyst treatment, and consumption is that 0.3～3% of dry recrement 1 weight adds catalyst; Dry recrement 1: polymer weight ratio is 3～1: 1 mixing; Discharge the air of reactor; Carry out cracking reaction at 400～550 ℃, the reaction time is 0.5～3 hour;
The 3rd step: gaseous product is collected on cracking limit, limit.The hydrocarbon gas that contains C1～C4 obtains liquefiable gas through cryogenic condensation; Product liquid is collected on cracking limit, limit, and product liquid is collected through after the condenser condenses.Obtain the hydrocarbon liquids product through layering again; And obtain recrement 2.
The 4th step: the gas of not liquefiable imports the combustion chamber, for copyrolysis provides energy; Product liquid obtains hydrocarbon liquids product and water soluble organic substance through layering.Water soluble organic substance obtains different oxygen-bearing organic matters through upgrading.
The 5th step: recrement 2 is heated to 650 degree, 2 hours in quartz reactor.Gas can be collected with preceding cracked gas and merge.Obtain the canescence silicide.
The conversion ratio of the total mixed waste of the present invention reaches 85～95%, hydrocarbon-containifirst gas comprises 15～22% in the output aggregate, hydrocarbon compound liquid 38～56%, oxygen-bearing organic matter 19～25%, silicide 10～15%.
Embodiment 2
According to preparation process and the method for embodiment 1, copyrolysis carries out in the synthesis under normal pressure device.Rice husk removes foreign matter, pulverizes, and gets 0.1 kilogram, with carrene-1.5 kilograms of extractings of alcohol, uses 1 kilogram hot-water extraction again, obtains biological active matter and recrement 1 after concentrating.Recrement 1 dries naturally, needs through catalyst treatment, presses 2.5% of recrement 1 weight and adds inorganic acid catalyst, adds the waste polypropylene of 0.7 kilogram of pulverizing.Emptying gas is warming up to 420 ℃, cracking 1 hour, and gaseous product is collected on cracking limit, limit, and the hydrocarbon gas that contains C1～C4 obtains liquefiable gas through cryogenic condensation; Product liquid is collected on cracking limit, limit, and product liquid is collected through after the condenser condenses, obtains the hydrocarbon liquids product through layering again; Obtain water-soluble oxygen-bearing organic matter and recrement 2 simultaneously.Recrement 2 is heated to 650 ℃ in quartz reactor, 2 hours; Gas can be collected with preceding cracked gas and merge, and obtains the canescence silicide.Gas and product liquid are analyzed by gas chromatograph-mass spectrometer.The conversion ratio 90% of total mixed waste, hydrocarbon gas accounts for 20% in the output aggregate, hydrocarbon liquids 50%, oxygen-bearing organic matter 10%, white silicide 10%.
Embodiment 3
According to preparation process and the method for embodiment 1, copyrolysis carries out in normal-pressure reaction kettle.0.1 kilogram in dry bamboo powder is used 1.5 kilograms hot-water extraction again with carrene-1.2 kilograms of extractings of alcohol, obtains biological active matter and recrement 1 after concentrated.Recrement 1 dries naturally, needs through catalyst treatment, presses 3% of recrement 1 weight and adds inorganic base catalyst, adds the waste polyethylene of 0.8 kilogram of pulverizing.Emptying gas is warming up to 520 ℃, cracking 2 hours.Gaseous product is collected on cracking limit, limit, and the hydrocarbon gas that contains C1～C4 obtains liquefiable gas through cryogenic condensation; Product liquid is collected on cracking limit, limit, and product liquid is collected through after the condenser condenses, obtains the hydrocarbon liquids product through layering again; Obtain water-soluble oxygen-bearing organic matter and recrement 2 simultaneously.Recrement 2 is heated to 650 ℃ in quartz reactor, 2 hours; Gas can be collected with preceding cracked gas and merge, and obtains the canescence silicide.Gas and product liquid are analyzed by gas chromatograph-mass spectrometer.The conversion ratio 87% of total mixed waste, hydrocarbon gas accounts for 18% in the output aggregate, hydrocarbon liquids 46%, oxygen-bearing organic matter 12%, white silicide 12%.
The present invention is subsidized by Zhejiang Province's plan of science and technology (2005C12023)
Claims (6)
1. one kind to being rich in the biomass castoff comprehensive utilization method of silicon, it is characterized in that at first the living beings in the agriculture and forestry organic waste material obtaining the biological active matter of different purposes with carrene-pure and mild hot-water extraction; Remaining thing after the extracting is high molecular cellulose, lignin and mineral matter, through catalyst treatment, obtain lysate with the polymer discarded object by cracking reaction in normal pressure reactor, the residue of cracking reaction remainder obtains silicide through handling, and preparation process is as follows:
1), will be rich in the biomass castoff of silicon, the agricultural processing waste that comprises rice husk, rice bar, bamboo class, wheat straw, it is dry to go foreign matter to pulverize, by dried biomass: carrene-pure weight ratio is 1: 10～20 extractings, use dried biomass again: 1: 5～15 extractings of hot water weight ratio, extract concentrates, the recrement after acquisition biological active matter and the extracting;
2), with the polymer discarded object, comprise polystyrene, polyethylene, polypropylene, damaged tire and daily waste plastic, it is dry to go foreign matter to pulverize, recrement after the extracting in the step 1) is dried naturally, recrement by drying: polymer weight ratio is 3～1: 1 mixing, add inorganic acid or inorganic base catalyst by 0.3～3% of dry recrement raw material weight, enter in the reactor by feeder; Discharge the air in the reactor, the vacuum anaerobic under normal pressure, is warming up to 400～550 ℃ and carries out cracking reaction;
3), cracking limit, limit collects gaseous product, the hydrocarbon gas that contains C1～C4 obtains liquefiable gas through cryogenic condensation; The gas of not liquefiable imports the combustion chamber, for cracking provides energy;
4), product liquid is collected, product liquid process layering acquisition hydrocarbon liquids product and water soluble organic substance in cracking limit, limit; Water soluble organic substance obtains different oxygen-bearing organic matters through after the upgrading;
5), the cracking reaction time is 0.5～3 hour, after reaction finishes, with the residue of cracking reaction remainder, is heated to 650 degree in quartz reactor, reacts 2 hours, obtains the canescence silicide.
2. pair be rich in the biomass castoff comprehensive utilization method of silicon according to claim 1, it is characterized in that raw material is rich in the biomass castoff of silicon, the polymer discarded object is ground into the particle less than 5mm.
3. pair be rich in the biomass castoff comprehensive utilization method of silicon according to claim 1, it is characterized in that the cracking reaction temperature is 450～520 ℃; The cracking reaction time is 1～2.5 hour.
4. pair be rich in the biomass castoff comprehensive utilization method of silicon according to claim 1, it is characterized in that lysate is gas hydro carbons, oily hydro carbons or oxygen-bearing organic matter.
5. pair be rich in the biomass castoff comprehensive utilization method of silicon according to claim 1, it is characterized in that silicide is for containing silica product.
6. pair be rich in the biomass castoff comprehensive utilization method of silicon according to claim 1, it is characterized in that catalyst is inorganic acid, inorganic base, consumption is 2% of a dry recrement raw material weight.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686624A (en) * | 2005-04-29 | 2005-10-26 | 刘文治 | Household gabbage chemical stability treatment technology |
| CN101343543A (en) * | 2008-07-09 | 2009-01-14 | 丽水市伟达新能源科技有限公司 | Comprehensive utilization method for agricultural wastes and plastic garbage |
| CN101352721A (en) * | 2007-07-23 | 2009-01-28 | 周鼎力 | Method for sequentially processing consumer waste |
| CN100513337C (en) * | 2006-07-28 | 2009-07-15 | 中国石油天然气股份有限公司 | Resource treating method for oil-containing sludge |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686624A (en) * | 2005-04-29 | 2005-10-26 | 刘文治 | Household gabbage chemical stability treatment technology |
| CN100513337C (en) * | 2006-07-28 | 2009-07-15 | 中国石油天然气股份有限公司 | Resource treating method for oil-containing sludge |
| CN101352721A (en) * | 2007-07-23 | 2009-01-28 | 周鼎力 | Method for sequentially processing consumer waste |
| CN101343543A (en) * | 2008-07-09 | 2009-01-14 | 丽水市伟达新能源科技有限公司 | Comprehensive utilization method for agricultural wastes and plastic garbage |
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