CN101503338A - Rapid liquefaction method for corps wastes by microwave heating catalysis - Google Patents
Rapid liquefaction method for corps wastes by microwave heating catalysis Download PDFInfo
- Publication number
- CN101503338A CN101503338A CNA2009100801812A CN200910080181A CN101503338A CN 101503338 A CN101503338 A CN 101503338A CN A2009100801812 A CNA2009100801812 A CN A2009100801812A CN 200910080181 A CN200910080181 A CN 200910080181A CN 101503338 A CN101503338 A CN 101503338A
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- China
- Prior art keywords
- microwave heating
- waste material
- microwave
- liquefaction
- agricultural waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 238000010438 heat treatment Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002699 waste material Substances 0.000 title abstract description 9
- 238000006555 catalytic reaction Methods 0.000 title description 5
- 208000031968 Cadaver Diseases 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 240000008042 Zea mays Species 0.000 claims description 38
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- 239000010902 straw Substances 0.000 claims description 31
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 24
- 235000009973 maize Nutrition 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- 239000002154 agricultural waste Substances 0.000 claims description 16
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 14
- 235000005822 corn Nutrition 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 241000209140 Triticum Species 0.000 claims description 5
- 235000021307 Triticum Nutrition 0.000 claims description 5
- -1 poly(oxyethylene glycol) Polymers 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 37
- 239000002028 Biomass Substances 0.000 description 11
- 150000005846 sugar alcohols Polymers 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a method for catalyzing waste of crops to be liquefied by microwave heating, which comprises: the waste of crops is added into polylol and sulphuric acid for microwave heating, the temperature is controlled to be 150-180 DEG C, and the liquification reaction is carried out for 10-30min. The method utilizes microwave auxiliary heating and reaction catalytic effect to realize rapid liquification for the waste of crops, thus greatly improving the liquification efficiency of the waste of crops and the liquification effect thereof, and leading the liquification efficiency to reach over 90%; the operation of the method is rapid, simple and convenient as well as efficient, so that the liquification cost of the waste of crops can be greatly reduced.
Description
Technical field
The present invention relates to the method that agricultural waste material utilizes, specifically, relate to a kind of method for preparing biomass polyalcohol that the agricultural waste material fast liquefying also can be improved greatly the liquefaction effect.
Background technology
Along with society growing to energy demand, the main energy sources fossil oil is in rapid minimizing.Therefore, countries in the world begin the development and use of extensive concern agricultural-forestry biomass resource, to substitute traditional energy.
China is a large agricultural country, and agricultural straw resource is very abundant, and reserves are very big, and the stalk output of China in 2005 is above 6.68 hundred million tons.Along with the variation of development of rural economy, energy structure and rural area resident population and labor force's minimizing, significantly reduce as the stalk of life in the countryside with energy, increasing stalk is directly incinerated, and has caused the serious environmental pollution.Demand developing the new way and the novel method of straw utilization urgently, to change current energy shortage and environmental pollution and a large amount of idle contradiction of wasting of stalk resource.
Though the stalk fibre raw material has the physicochemical property of relative ideals such as storing energy, renewable, easy decomposition, because little, the characteristics such as calorific value is low, indissoluble, infusibility of density are difficult to direct utilization; With the agricultural crop straw is raw material, after liquefaction under certain technical qualification, become the fluent meterial that contains great amount of hydroxy group with high reaction activity, it is biomass polyalcohol, be used for synthetic various macromolecular materials to substitute traditional industrial chemicals, be subjected to extensive concern in recent years, the agricultural crop straw liquefaction technology has not only been opened up the new way of agriculture and forestry organic waste material comprehensive utilization, and help the dependence of alleviation to the petrochemical industry resource, reduce environmental pollution.
Liquefaction technology for straw biomass mainly adopts the liquefaction of oil bath heating (90～200 ℃) catalysis stalk at present, liquefying time is longer, generally need 1～2 hour (CN101172932A, CN101186559A, CN101186560A etc.), the liquefaction yield only is 60～70% when adopting cheap ethylene glycol for liquefying agent, adopt higher polyoxyethylene glycol of price or NSC 11801 liquefaction yield also only can reach 80～90%, therefore there are shortcomings such as liquefying time is long, efficient is low, cost height in traditional liquefaction technology, is unfavorable for large-scale application.
Summary of the invention
Problems such as it is long to the objective of the invention is to solve the conventional heating of agricultural waste material liquefying time, and liquefied fraction is low, the method that provides a kind of corps wastes by microwave heating catalysis to liquefy rapidly and efficiently liquefies agricultural waste material with realization.
In order to realize the object of the invention, the method of a kind of corps wastes by microwave heating catalysis liquefaction of the present invention, the method comprising the steps of: agricultural waste material is joined in polyvalent alcohol and the sulfuric acid microwave heating, controlled temperature is at 150～180 ℃, liquefaction reaction 10～30 minutes.
Wherein, described agricultural waste material is maize straw, wheat stalk, rice straw, cotton stalk or corn cob.
Described agricultural waste material can be crushed to 20～100 orders earlier.
The present invention can select the microwave heating installation of airtight temperature control, adjustable power for use, and microwave power is controlled at 400～1000W.
Described polyvalent alcohol is a liquefying agent, adopts ethylene glycol, or the mixture of poly(oxyethylene glycol) 400 and glycerine volume ratio 4:1.
Described agricultural waste material add-on accounts for 20～30% of described polyvalent alcohol weight.
Described sulfuric acid is catalyzer, is good with 98% vitriol oil, and its add-on is 3～5% of a described polyvalent alcohol weight.
The present invention adopts the microwave-assisted heating technique is incorporated in the liquefaction of agricultural waste material, heated by microwave and katalysis, can be fast with the material heating and be that liquefaction reaction is played katalysis.Through microwave heating and conventional oil bath are compared, find to adopt the liquefied fraction of the liquefied fraction of microwave heating, as shown in Figure 1 apparently higher than conventional oil bath.Therefore, the present invention can overcome the deficiency that liquefying time is long and liquefied fraction is low in the conventional oil bath heating liquefaction, reaches at short notice the effect of agricultural waste material fast liquefying, and liquefied fraction reaches more than 90%.This method operation is quick, easy, efficient, has greatly reduced the cost of agricultural waste material liquefaction.
Description of drawings
Fig. 1 prepares the effect comparison diagram of polyvalent alcohol for respectively maize straw being liquefied with microwave heating and oil bath heating.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Maize straw is crushed to 40 orders, take by weighing corn stalk powder 6g and add the liquefying agent ethylene glycol 20g and 0.7g catalyzer 98% vitriol oil, be that the stalk quality is 30% of a liquefying agent quality, the vitriol oil is 3.5% of a liquefying agent quality, set 160 ℃ of microwave temperature, microwave power 600W adopts the closed microwave heating, magnetic agitation liquefaction reaction 25 minutes obtains maize straw liquefied product biomass polyalcohol.
After testing, the liquefied fraction of maize straw reaches 94.6% under this liquefaction condition.
Embodiment 2
Maize straw is crushed to 40 orders, add liquefying agent poly(oxyethylene glycol) 400 and glycerine 4:1 (v/v) mixture and catalyzer 98% vitriol oil in the corn stalk powder, the liquefying agent quality is 25g, the stalk quality is 20% of a liquefying agent quality, and the vitriol oil is 3.5% of a liquefying agent quality, sets 150 ℃ of microwave temperature, microwave power 400W, adopt closed microwave heating, magnetic agitation liquefaction reaction 20 minutes obtains maize straw liquefied product biomass polyalcohol.
After testing, the liquefied fraction of maize straw reaches 92.4% under this liquefaction condition.
Embodiment 3
Corn cob meal is broken to 40 orders, add the liquefying agent ethylene glycol and catalyzer 98% vitriol oil in the corn cob meal, the liquefying agent quality is 250g, the corn cob quality is 20% of a liquefying agent quality, and the vitriol oil is 5.0% of a liquefying agent quality, sets 150 ℃ of microwave temperature, microwave power 1000W, adopt closed microwave heating, magnetic agitation liquefaction reaction 20 minutes obtains corn cob liquefied product biomass polyalcohol.The liquefied fraction of corn cob reaches 91.5% under this liquefaction condition.
Embodiment 4
Wheat stalk is crushed to 20 orders, add the liquefying agent ethylene glycol and catalyzer 98% vitriol oil in the wheat stalk powder, the liquefying agent quality is 25g, the stalk quality is 20% of a liquefying agent quality, and the vitriol oil is 3.5% of a liquefying agent quality, sets 160 ℃ of microwave temperature, microwave power 600W, adopt closed microwave heating, magnetic agitation liquefaction reaction 20 minutes obtains wheat stalk liquefied product biomass polyalcohol.The liquefied fraction of maize straw reaches 92.2% under this liquefaction condition.
Embodiment 5
Maize straw is crushed to 40 orders, add the liquefying agent ethylene glycol and catalyzer 98% vitriol oil in the corn stalk powder, the liquefying agent quality is 25g, the stalk quality is 25% of a liquefying agent quality, and the vitriol oil is 3.0% of a liquefying agent quality, sets 180 ℃ of microwave temperature, microwave power 600W, adopt closed microwave heating, magnetic agitation liquefaction reaction 30 minutes obtains maize straw liquefied product biomass polyalcohol.The liquefied fraction of maize straw reaches 96.5% under this liquefaction condition.
Embodiment 6
Maize straw is crushed to 100 orders, add the liquefying agent ethylene glycol and catalyzer 98% vitriol oil in the corn stalk powder, the liquefying agent quality is 25g, the stalk quality is 20% of a liquefying agent quality, and the vitriol oil is 3.0% of a liquefying agent quality, sets 180 ℃ of microwave temperature, microwave power 600W, adopt closed microwave heating, magnetic agitation liquefaction reaction 10 minutes obtains maize straw liquefied product biomass polyalcohol.The liquefied fraction of maize straw reaches 91.2% under this liquefaction condition.
Embodiment 7
Maize straw is crushed to 40 orders, add the liquefying agent ethylene glycol and catalyzer 98% vitriol oil in the corn stalk powder, the liquefying agent quality is 25g, the stalk quality is 20% of a liquefying agent quality, and the vitriol oil is 3.5% of a liquefying agent quality, sets 180 ℃ of microwave temperature, microwave power 600W, adopt closed microwave heating, magnetic agitation liquefaction reaction 20 minutes obtains maize straw liquefied product biomass polyalcohol.The liquefied fraction of maize straw reaches 97.1% under this liquefaction condition.
The test example
Maize straw is crushed to 40 orders, adds the liquefying agent ethylene glycol and catalyzer 98% vitriol oil in the corn stalk powder, the liquefying agent quality is 25g, the stalk quality is 30% of a liquefying agent quality, and the vitriol oil is 3.5% of a liquefying agent quality, sets 160 ℃ of microwave temperature, microwave power 600W adopts closed microwave heating, and magnetic agitation is liquefaction reaction 5 respectively, 10,15,20,25,30 minutes, obtain different microwave heating liquefying time maize straw liquefied fractions such as Fig. 1.
Maize straw is crushed to 40 orders, add the liquefying agent ethylene glycol and catalyzer 98% vitriol oil in the corn stalk powder, the liquefying agent quality is 25g, and the stalk quality is 30% of a liquefying agent quality, and the vitriol oil is 3.5% of a liquefying agent quality, set 160 ℃ of oil bath temperatures, mechanical stirring is liquefaction reaction 30,60,90 respectively, 120 minutes, obtain maize straw liquefied fraction such as Fig. 1 that liquefying times are heated in different oil baths.
As can be seen from Figure 1 microwave heating can be liquefied the maize straw more than 90% with interior at 30 minutes, and 1～2 hour liquefied fraction of oil bath heating liquefaction is also only about 70%, therefore microwave heating liquefaction can be shortened liquefying time greatly, significantly improving liquefaction efficiency, is a kind of liquifying method rapidly and efficiently.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (7)
1. the liquifying method of an agricultural waste material is characterized in that, comprises step: agricultural waste material is joined in polyvalent alcohol and the sulfuric acid, and microwave heating, controlled temperature is at 150～180 ℃, liquefaction reaction 10～30 minutes.
2. liquifying method according to claim 1 is characterized in that, described agricultural waste material is maize straw, wheat stalk, rice straw, cotton stalk or corn cob.
3. liquifying method according to claim 1 and 2 is characterized in that microwave heating is controlled at 400～1000W with the power of microwave device.
4. liquifying method according to claim 3 is characterized in that, described polyvalent alcohol is an ethylene glycol, or is the mixture of poly(oxyethylene glycol) 400 and glycerine volume ratio 4:1.
5. according to claim 1,2 or 4 described liquifying methods, it is characterized in that described agricultural waste material add-on is 20～30% of a polyvalent alcohol weight.
6. liquifying method according to claim 5 is characterized in that, described sulfuric acid is 98% vitriol oil, and its add-on is 3～5% of a described polyvalent alcohol weight.
7. according to claim 1,2 or 4 described liquifying methods, it is characterized in that described agricultural waste material is crushed to 20～100 orders earlier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100801812A CN101503338B (en) | 2009-03-25 | 2009-03-25 | Rapid liquefaction method for corps wastes by microwave heating catalysis |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100801812A CN101503338B (en) | 2009-03-25 | 2009-03-25 | Rapid liquefaction method for corps wastes by microwave heating catalysis |
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| Publication Number | Publication Date |
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| CN101503338A true CN101503338A (en) | 2009-08-12 |
| CN101503338B CN101503338B (en) | 2012-07-25 |
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| CN2009100801812A Expired - Fee Related CN101503338B (en) | 2009-03-25 | 2009-03-25 | Rapid liquefaction method for corps wastes by microwave heating catalysis |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011028645A1 (en) * | 2009-09-03 | 2011-03-10 | The Ohio State University Research Foundation | Methods for producing polyols and polyurethanes |
| CN102181030A (en) * | 2011-04-07 | 2011-09-14 | 中国农业大学 | Method for preparing corncob-base polyurethane rigid foam damping material |
| CN102320921A (en) * | 2011-05-12 | 2012-01-18 | 中科院广州化学有限公司 | Method for preparing biomass polylol by using ultrasonic waves and application thereof |
| CN104140538A (en) * | 2013-05-09 | 2014-11-12 | 中国林业科学研究院木材工业研究所 | Continuous biomass liquefaction method |
| CN104163762A (en) * | 2014-07-29 | 2014-11-26 | 中国农业大学 | Method for synthesis of acetyl propionate through microwave assisted liquefaction of biomass straw |
| CN107029727A (en) * | 2016-02-04 | 2017-08-11 | 中国人民大学 | A kind of catalyst of catalytically liquefying biomass oil and preparation method and application |
| CN107029730A (en) * | 2016-02-04 | 2017-08-11 | 中国人民大学 | A kind of titanium dichloride load thulium Raney nickel and preparation method and application |
-
2009
- 2009-03-25 CN CN2009100801812A patent/CN101503338B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011028645A1 (en) * | 2009-09-03 | 2011-03-10 | The Ohio State University Research Foundation | Methods for producing polyols and polyurethanes |
| US8022257B2 (en) | 2009-09-03 | 2011-09-20 | The Ohio State University Research Foundation | Methods for producing polyols using crude glycerin |
| CN102181030A (en) * | 2011-04-07 | 2011-09-14 | 中国农业大学 | Method for preparing corncob-base polyurethane rigid foam damping material |
| CN102181030B (en) * | 2011-04-07 | 2012-09-26 | 中国农业大学 | Method for preparing corncob-base polyurethane rigid foam damping material |
| CN102320921A (en) * | 2011-05-12 | 2012-01-18 | 中科院广州化学有限公司 | Method for preparing biomass polylol by using ultrasonic waves and application thereof |
| CN104140538A (en) * | 2013-05-09 | 2014-11-12 | 中国林业科学研究院木材工业研究所 | Continuous biomass liquefaction method |
| CN104140538B (en) * | 2013-05-09 | 2016-08-10 | 中国林业科学研究院木材工业研究所 | A kind of continuous biomass liquifying method |
| CN104163762A (en) * | 2014-07-29 | 2014-11-26 | 中国农业大学 | Method for synthesis of acetyl propionate through microwave assisted liquefaction of biomass straw |
| CN107029727A (en) * | 2016-02-04 | 2017-08-11 | 中国人民大学 | A kind of catalyst of catalytically liquefying biomass oil and preparation method and application |
| CN107029730A (en) * | 2016-02-04 | 2017-08-11 | 中国人民大学 | A kind of titanium dichloride load thulium Raney nickel and preparation method and application |
| CN107029727B (en) * | 2016-02-04 | 2020-02-14 | 中国人民大学 | Catalyst for catalytic liquefaction of biomass oil and preparation method and application thereof |
| CN107029730B (en) * | 2016-02-04 | 2020-02-14 | 中国人民大学 | Titanium dioxide loaded thulium-nickel catalyst and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN101503338B (en) | 2012-07-25 |
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