CN102676242A - 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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- CN102676242A CN102676242A CN2012101795350A CN201210179535A CN102676242A CN 102676242 A CN102676242 A CN 102676242A CN 2012101795350 A CN2012101795350 A CN 2012101795350A CN 201210179535 A CN201210179535 A CN 201210179535A CN 102676242 A CN102676242 A CN 102676242A
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- China
- Prior art keywords
- agriculture
- solid acid
- organic waste
- waste material
- forestry organic
- Prior art date
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000011973 solid acid Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000007171 acid catalysis Methods 0.000 title claims abstract description 11
- 239000003225 biodiesel Substances 0.000 title abstract description 6
- 239000002699 waste material Substances 0.000 title abstract description 5
- 238000000197 pyrolysis Methods 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 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 22
- 239000010815 organic waste Substances 0.000 claims description 22
- 239000002551 biofuel Substances 0.000 claims description 13
- 239000012263 liquid product Substances 0.000 claims description 12
- 238000005336 cracking Methods 0.000 claims description 11
- 239000012075 bio-oil Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000002916 wood waste Substances 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
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000005516 engineering process Methods 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
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa 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
- 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
- 230000000813 microbial effect Effects 0.000 description 1
- 239000010773 plant oil Substances 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 prepare method of bio-diesel oil, particularly supercritical methanol microwave cracking solid acid catalysis agriculture and forestry organic waste material prepares the method for bio oil, belongs to the bioenergy technical field.
Background technology
At present, the tankage that biofuel is mainly processed with various animal-plant oil, microbial oil, discarded food and drink oil, vegetables oil etc. are feedstock production, prepare through transesterification reaction.75% is raw materials cost in the biodiesel manufacture cost, and the price height is the commercial major obstacle of biofuel alternative fuel, seek cheap raw material and efficiently the biofuel processing technology become the key of biofuel industrialized development.In China, the output of annual various agriculture and forestry organic waste materials is considerable, and these feedstock production are become biofuel, and can be these waste recycle provides outlet on the one hand, has also solved the raw material problem of biofuel simultaneously.
Summary of the invention
For problems such as solution biodiesel manufacture cost height, 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, realize through following technical proposal.
A kind of supercritical methanol microwave cracking solid acid catalysis agriculture and forestry organic waste material prepares the method for bio oil, following each step of process:
(1) by mass ratio the mixed of 100 ︰ 20～30 with agriculture and forestry organic waste material and the methyl alcohol pulverized; 2～5% the solid acid catalyst that adds the agriculture and forestry organic waste material quality again is that 250～350 ℃, reaction pressure are to carry out microwave heating 30～60 minutes under the condition of 10～15MPa in temperature of reaction then;
(2) after reaction finishes step (1) products therefrom is isolated liquid product and unreacted raw material through filtration, promptly obtain biofuel (fatty acid methyl ester) after the methyl alcohol of liquid product is reclaimed.
The agriculture and forestry organic waste material of said step (1) is agricultural crop straw (like wheat stalk, corn straw, paddy stalk etc.), agriculture industrial wood waste (like rice husk, bagasse, corn cob etc.), sawdust.
The pulverizing of said step (1) is that agriculture and forestry organic waste material is crushed to 50～100 orders.
The solid acid catalyst of said 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
3The type solid acid.
The microwave heating of said step (1) is to be that 500～1000W, frequency are to carry out under the microwave condition of 50Hz at power.
Advantage of the present invention and positively effect:
The present invention organically combines microwave cracking and supercritical methanol esterification, utilizes microwave cracking to have characteristics fast on the one hand, simultaneously the timely esterification of split product is obtained biofuel at cracked on the other hand; It is simple to have technology; Advantages such as the reaction times is short, and efficient is high, and raw materials cost is low.
Embodiment
Further specify flesh and blood of the present invention with instance below, but content of the present invention is not limited to this.
Embodiment 1
(1) will be crushed to 50 purpose wheat stalks, with methyl alcohol be the mixed of 100 ︰ 20 by mass ratio, add 2% solid acid catalyst SO of agriculture and forestry organic waste material quality again
4 2-/ ZrO
2The type solid acid is that 250 ℃, reaction pressure are under the 10MPa to be that 500W, frequency are that the microwave condition of 50Hz carried out microwave heating 30 minutes with power in temperature of reaction then;
(2) after reaction finishes step (1) products therefrom is isolated liquid product and unreacted raw material through filtration, promptly obtain biofuel (fatty acid methyl ester) after the methyl alcohol of liquid product is reclaimed.
Embodiment 2
(1) will be crushed to 80 purpose bagasses and methyl alcohol is the mixed of 100 ︰ 25 by mass ratio, adds 3% solid acid catalyst SO of agriculture and forestry organic waste material quality again
4 2-/ TiO
2The type solid acid is that 300 ℃, reaction pressure are under the 12MPa to be that 800W, frequency are that the microwave condition of 50Hz carried out microwave heating 60 minutes with power in temperature of reaction then;
(2) after reaction finishes step (1) products therefrom is isolated liquid product and unreacted raw material through filtration, promptly obtain biofuel (fatty acid methyl ester) after the methyl alcohol of liquid product is reclaimed.
Embodiment 3
(1) will be crushed to 100 purpose sawdusts and methyl alcohol is the mixed of 100 ︰ 30 by mass ratio, adds 2% solid acid catalyst SO of agriculture and forestry organic waste material quality again
4 2-/ ZrO
2-TiO
2The type solid acid is that 350 ℃, reaction pressure are under the 15MPa to be that 1000W, frequency are that the microwave condition of 50Hz carried out microwave heating 50 minutes with power in temperature of reaction then;
(2) after reaction finishes step (1) products therefrom is isolated liquid product and unreacted raw material through filtration, promptly obtain biofuel (fatty acid methyl ester) after the methyl alcohol of liquid product is reclaimed.
Embodiment 4
(1) will be crushed to 60 purpose paddy stalks and methyl alcohol is the mixed of 100 ︰ 25 by mass ratio, adds 5% solid acid catalyst SO of agriculture and forestry organic waste material quality again
4 2-/ TiO
2-Fe
2O
3The type solid acid is that 300 ℃, reaction pressure are under the 12MPa to be that 800W, frequency are that the microwave condition of 50Hz carried out microwave heating 40 minutes with power in temperature of reaction then;
(2) after reaction finishes step (1) products therefrom is isolated liquid product and unreacted raw material through filtration, promptly obtain biofuel (fatty acid methyl ester) after the methyl alcohol of liquid product is reclaimed.
Claims (5)
1. a supercritical methanol microwave cracking solid acid catalysis agriculture and forestry organic waste material prepares the method for bio oil, it is characterized in that through following each step:
(1) by mass ratio the mixed of 100 ︰ 20～30 with agriculture and forestry organic waste material and the methyl alcohol pulverized; 2～5% the solid acid catalyst that adds the agriculture and forestry organic waste material quality again is that 250～350 ℃, reaction pressure are to carry out microwave heating 30～60 minutes under the condition of 10～15MPa in temperature of reaction then;
(2) after reaction finishes step (1) products therefrom is isolated liquid product and unreacted raw material through filtration, promptly obtain biofuel after the methyl alcohol of liquid product is reclaimed.
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 said step (1) is agricultural crop straw, agriculture industrial wood waste, sawdust.
3. 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 pulverizing of said step (1) is that agriculture and forestry organic waste material is crushed to 50～100 orders.
4. 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 solid acid catalyst of said 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
3The type solid acid.
5. 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 microwave heating of said step (1) is to be that 500～1000W, frequency are to carry out under the microwave condition of 50Hz at power.
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 true CN102676242A (en) | 2012-09-19 |
| CN102676242B CN102676242B (en) | 2015-05-13 |
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|---|---|---|---|
| CN201210179535.0A Active 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 |
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| CN (1) | CN102676242B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2020228488A1 (en) * | 2019-05-14 | 2020-11-19 | 南京科津新材料研究院有限公司 | Method for comprehensive utilization of biomass 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 |
-
2012
- 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 |
|---|
| JEEBAN POUDEL ET AL.: "A kinetic analysis of wood degradation in supercritical alcohols", 《IND.ENG.CHEM.RES.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2020228488A1 (en) * | 2019-05-14 | 2020-11-19 | 南京科津新材料研究院有限公司 | Method for comprehensive utilization of biomass material |
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| Publication number | Publication date |
|---|---|
| CN102676242B (en) | 2015-05-13 |
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