CN102676242B - Method for preparing biodiesel fuel by conducting supercritical methanol microwave pyrolysis and solid acid catalysis on agriculture and forestry waste - Google Patents
Method for preparing biodiesel fuel by conducting supercritical methanol microwave pyrolysis and solid acid catalysis on agriculture and forestry waste Download PDFInfo
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- CN102676242B CN102676242B CN201210179535.0A CN201210179535A CN102676242B CN 102676242 B CN102676242 B CN 102676242B CN 201210179535 A CN201210179535 A CN 201210179535A CN 102676242 B CN102676242 B CN 102676242B
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- agriculture
- solid acid
- reaction
- organic waste
- forestry organic
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011973 solid acid Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000007171 acid catalysis Methods 0.000 title claims abstract description 8
- 239000002699 waste material Substances 0.000 title abstract description 5
- 238000000197 pyrolysis Methods 0.000 title abstract 4
- 239000003225 biodiesel Substances 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 18
- 239000010815 organic waste Substances 0.000 claims description 18
- 239000002551 biofuel Substances 0.000 claims description 15
- 239000012263 liquid product Substances 0.000 claims description 12
- 238000005336 cracking Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 239000012075 bio-oil Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 3
- 238000003754 machining Methods 0.000 claims description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 6
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 241000609240 Ambelania acida Species 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention relates to a method for preparing a biodiesel fuel by conducting supercritical methanol microwave pyrolysis and solid acid catalysis on agriculture and forestry waste. The agriculture and forestry waste and methanol are mixed according to the mass ratio of 100 : (20 to 30); adding solid acid catalyst of which the weight is 2 to 5 wt% that of the agriculture and forestry waste; carrying out micro-wave heating pyrolysis; controlling the reaction temperature to be 250 to 350 DEG C, the reaction pressure to be 10 to 15 MPa, and the reaction time to be 30 to 60 min; and still standing and carrying out separation and methanol recovery after the reaction, so as to obtain fatty acid methyl ester (namely the biodiesel fuel). As microwave pyrolysis and supercritical methanol esterification reaction are combined organically, the method has the advantages that the process is simple; the reaction time is short; the efficiency is high; and the raw material cost is low.
Description
Technical field
The present invention relates to the method preparing biofuel, particularly supercritical methanol microwave cracking solid acid catalysis agriculture and forestry organic waste material prepares the method for bio oil, belongs to bioenergy technical field.
Background technology
At present, biofuel mainly with the tankage of various animal-plant oil, microbial oil, discarded food and drink oil, vegetables oil processing etc. for prepared by raw material, prepare through transesterification reaction.In biofuel preparation cost, 75% is raw materials cost, and price height is the commercial major obstacle of biofuel alternative fuel, seeks the key that cheap raw material and efficient biofuel processing technology become Biodieselization development.In China, the output of annual various agriculture and forestry organic waste material is considerable, and these raw materials are prepared into biofuel, and the recycling that can be these wastes on the one hand provides outlet, also solves the raw material problem of biofuel simultaneously.
Summary of the invention
For solving the problems such as biofuel preparation cost is high, the object of the present invention is to provide a kind of supercritical methanol microwave cracking solid acid catalysis agriculture and forestry organic waste material to prepare the method for bio oil, being realized by following technical proposal.
Supercritical methanol microwave cracking solid acid catalysis agriculture and forestry organic waste material prepares a method for bio oil, through following each step:
(1) ratio being 100 ︰ 20 ~ 30 in mass ratio by the agriculture and forestry organic waste material of pulverizing and methyl alcohol mixes, add the solid acid catalyst of 2 ~ 5% of agriculture and forestry organic waste material quality again, then temperature of reaction be 250 ~ 350 DEG C, reaction pressure carries out microwave heating 30 ~ 60 minutes under being the condition of 10 ~ 15MPa;
(2) step (1) products therefrom is separated by filtration out liquid product and unreacted raw material after terminating by reaction, namely obtains biofuel (fatty acid methyl ester) after being reclaimed by the methyl alcohol of liquid product.
The agriculture and forestry organic waste material of described step (1) is agricultural crop straw (as wheat stalk, maize straw, paddy stalk etc.), agricultural machining residuum (as rice husk, bagasse, corn cob etc.), sawdust.
The pulverizing of described step (1) is that agriculture and forestry organic waste material is crushed to 50 ~ 100 orders.
The solid acid catalyst of described step (1) is SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2-TiO
2, SO
4 2-/ TiO
2-Fe
2o
3type solid acid.
The microwave heating of described step (1) be power be 500 ~ 1000W, frequency carries out under being the microwave condition of 50Hz.
Advantage of the present invention and positively effect:
Microwave cracking and supercritical methanol esterification organically combine by the present invention, utilize microwave cracking to have feature fast on the one hand, while cracking, timely for split product esterification are obtained biofuel on the other hand, there is technique simple, the advantages such as the reaction times is short, and efficiency is high, and raw materials cost is low.
Embodiment
Further illustrate flesh and blood of the present invention with example below, but content of the present invention is not limited to this.
Embodiment 1
(1) will 50 object wheat stalks be crushed to, be that the ratio of 100 ︰ 20 mixes in mass ratio with methyl alcohol, then add agriculture and forestry organic waste material quality 2% solid acid catalyst SO
4 2-/ ZrO
2type solid acid, then carries out microwave heating 30 minutes at the microwave condition that temperature of reaction is 250 DEG C, reaction pressure is 500W with power under being 10MPa, frequency is 50Hz;
(2) step (1) products therefrom is separated by filtration out liquid product and unreacted raw material after terminating by reaction, namely obtains biofuel (fatty acid methyl ester) after being reclaimed by the methyl alcohol of liquid product.
Embodiment 2
(1) mix being crushed to the ratio that 80 object bagasses and methyl alcohol are 100 ︰ 25 in mass ratio, then add agriculture and forestry organic waste material quality 3% solid acid catalyst SO
4 2-/ TiO
2type solid acid, then carries out microwave heating 60 minutes at the microwave condition that temperature of reaction is 300 DEG C, reaction pressure is 800W with power under being 12MPa, frequency is 50Hz;
(2) step (1) products therefrom is separated by filtration out liquid product and unreacted raw material after terminating by reaction, namely obtains biofuel (fatty acid methyl ester) after being reclaimed by the methyl alcohol of liquid product.
Embodiment 3
(1) mix being crushed to the ratio that 100 object sawdusts and methyl alcohol are 100 ︰ 30 in mass ratio, then add agriculture and forestry organic waste material quality 2% solid acid catalyst SO
4 2-/ ZrO
2-TiO
2type solid acid, then carries out microwave heating 50 minutes at the microwave condition that temperature of reaction is 350 DEG C, reaction pressure is 1000W with power under being 15MPa, frequency is 50Hz;
(2) step (1) products therefrom is separated by filtration out liquid product and unreacted raw material after terminating by reaction, namely obtains biofuel (fatty acid methyl ester) after being reclaimed by the methyl alcohol of liquid product.
Embodiment 4
(1) mix being crushed to the ratio that 60 object paddy stalks and methyl alcohol are 100 ︰ 25 in mass ratio, then add agriculture and forestry organic waste material quality 5% solid acid catalyst SO
4 2-/ TiO
2-Fe
2o
3type solid acid, then carries out microwave heating 40 minutes at the microwave condition that temperature of reaction is 300 DEG C, reaction pressure is 800W with power under being 12MPa, frequency is 50Hz;
(2) step (1) products therefrom is separated by filtration out liquid product and unreacted raw material after terminating by reaction, namely obtains biofuel (fatty acid methyl ester) after being reclaimed by the methyl alcohol of liquid product.
Claims (2)
1. supercritical methanol microwave cracking solid acid catalysis agriculture and forestry organic waste material prepares a method for bio oil, it is characterized in that through following each step:
(1) mix being crushed to the ratio that 50 ~ 100 object agriculture and forestry organic waste materials and methyl alcohol are 100 ︰ 20 ~ 30 in mass ratio, add the solid acid catalyst of 2 ~ 5% of agriculture and forestry organic waste material quality again, then temperature of reaction be 250 ~ 350 DEG C, reaction pressure carries out microwave heating 30 ~ 60 minutes under being the condition of 10 ~ 15MPa, the power of microwave heating is 500 ~ 1000W, frequency is 50Hz, and wherein solid acid catalyst is SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2-TiO
2, SO
4 2-/ TiO
2-Fe
2o
3type solid acid;
(2) step (1) products therefrom is separated by filtration out liquid product and unreacted raw material after terminating by reaction, namely obtains biofuel after being reclaimed by the methyl alcohol of liquid product.
2. supercritical methanol microwave cracking solid acid catalysis agriculture and forestry organic waste material according to claim 1 prepares the method for bio oil, it is characterized in that: the agriculture and forestry organic waste material of described step (1) is agricultural crop straw, agricultural machining residuum, sawdust.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210179535.0A CN102676242B (en) | 2012-06-04 | 2012-06-04 | Method for preparing biodiesel fuel by conducting supercritical methanol microwave pyrolysis and solid acid catalysis on agriculture and forestry waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210179535.0A CN102676242B (en) | 2012-06-04 | 2012-06-04 | Method for preparing biodiesel fuel by conducting supercritical methanol microwave pyrolysis and solid acid catalysis on agriculture and forestry waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102676242A CN102676242A (en) | 2012-09-19 |
| CN102676242B true CN102676242B (en) | 2015-05-13 |
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| CN111100662B (en) * | 2018-10-29 | 2021-07-02 | 中国石油化工股份有限公司 | Continuous operation method for microwave pyrolysis of waste plastics |
| CN110093172A (en) * | 2019-05-14 | 2019-08-06 | 南京科津新材料研究院有限公司 | A kind of method of comprehensive utilization of biological material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810931A (en) * | 2006-02-22 | 2006-08-02 | 福建师范大学 | Microwave process to prepare biological diesel oil |
-
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- 2012-06-04 CN CN201210179535.0A patent/CN102676242B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1810931A (en) * | 2006-02-22 | 2006-08-02 | 福建师范大学 | Microwave process to prepare biological diesel oil |
Non-Patent Citations (1)
| Title |
|---|
| A kinetic analysis of wood degradation in supercritical alcohols;Jeeban Poudel et al.;《Ind.Eng.Chem.Res.》;20120102;第51卷;第4509-4510页） * |
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| CN102676242A (en) | 2012-09-19 |
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