CN102618392A - Method for synthetizing biodiesel from resin solid acid catalyzed waste oil - Google Patents
Method for synthetizing biodiesel from resin solid acid catalyzed waste oil Download PDFInfo
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- CN102618392A CN102618392A CN2012100830323A CN201210083032A CN102618392A CN 102618392 A CN102618392 A CN 102618392A CN 2012100830323 A CN2012100830323 A CN 2012100830323A CN 201210083032 A CN201210083032 A CN 201210083032A CN 102618392 A CN102618392 A CN 102618392A
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- solid acid
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- 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
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- 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
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Abstract
The invention discloses a method for synthetizing biodiesel from resin solid acid catalyzed waste oil, which belongs to the technical field of organic chemical synthesis. The method is characterized by including that waste oil serving as raw materials and resin solid acid serving as catalyst are subjected to transesterification reaction with low-grade fatty alcohol, after reaction, the catalyst is filtered from reaction mixture, and the biodiesel is obtained after skimming, rinsing, alkali cleaning and distilling. The method for synthetizing biodiesel from resin solid acid catalyzed waste oil has the following advantages of high yield and catalyzing efficiency and the like.
Description
Technical field:
The present invention relates to a kind of method of resin base solid acid catalysis waste grease biodiesel synthesis, belong to the organic chemistry synthesis technical field.
Background technology:
Along with the minimizing day by day of mineral wealth such as oil with and ball border influence over the ground, the green renewable fuel resource of development of new becomes the problem of present extensive concern.Biofuel is a kind of mono alkyl ester of longer chain fatty acid, not sulfur-bearing and aromatic hydrocarbons, and cetane value is high, and lubricity is good, is a kind of high-quality clean fuel.Simultaneously, biofuel has the incomparable advantage of traditional fossil fuel, and raw material is the grease of reproducible biomass; The environmental friendliness of product own, biodegradable, flash-point is high; Nontoxic, volatile organic matter (VOC) content is low, and calorific value is high, burning is complete; Need not change and frequent cleaned engine, also be to make biodegradable fine chemical product raw material with high added value.The of paramount importance environmental protection effect of biofuel is with a kind of indirect mode, changes hydrocarbon polymer again into through CO2, and the clean quantity discharged of CO2 is reduced greatly.Scientists thinks that after deliberation using the biomass material energy is that a kind of ratio increase forest reserves (absorbing as CO2) more have conduct and more effective strategy.The working method of biofuel mainly is that the transesterification reaction through vegetables oil or animal tallow and lower aliphatic alcohols prepares.Normally used catalyzer mainly contains acid catalysis, base catalysis, enzyme catalysis and supercritical methanol technology.Base catalysis [Sheng Mei etc., colleges and universities' chemical engineering journal, 2004; 18 (2): 231-236] many employing homogeneous catalysts such as NaOH, KOH, sodium methylate etc. exist the ingredient requirement strictness, need the severe condition of anhydrous anacidity; There is the saponification phenomenon simultaneously, shortcomings such as product aftertreatment complicacy.Enzyme catalysis [Nie Kaili etc., biological processing, 2005,3 (1): 58-62] exists catalyzer to cost an arm and a leg, easy inactivation, shortcomings such as long reaction time.Exist temperature of reaction and pressure to surpass the critical temperature and the emergent pressure of methyl alcohol with overcritical on-catalytic method, production technique is high to equipment requirements.Acid catalyzed process [Ono, Y.J. Catal, 2003,216 (1-2): 406] has the reactive behavior height, and is little to ingredient requirement, can be high acid value or aqueous raw oil, and do not have the generation of side reaction such as saponification.Uses liquid acid such as sulfuric acid to be catalyzer but tradition is many, exist equipment corrosion serious, catalyst separating is difficult, shortcoming such as can't reuse.As the maximum country of population owning amount; Waste cooking oil (being commonly called as rubbish oil, hogwash fat) is troubling problem always, is raw material with the food and beverage waste oil and grease, the preparation biofuel; Can benefit the nation and the people; Can solve above-mentioned pollution problem like this, can also turn waste into wealth, reduce the manufacturing cost of biofuel.
Summary of the invention:
The object of the present invention is to provide a kind of method of eco-friendly resin base solid acid catalysis waste grease biodiesel synthesis.
The present invention solves this technical problem through following technical scheme:
A kind of method of resin base solid acid catalysis waste grease biodiesel synthesis; It is characterized in that: be raw material with the waste grease; Adopt resin base solid acid as catalyst, carry out transesterification reaction, after reaction finishes with lower aliphatic alcohols; Catalyzer is filtered out from reaction mixture, handle to obtain biofuel through separatory, washing, alkali cleaning, distillation.
Further be provided with and be:
The mass ratio of said grease, lower aliphatic alcohols, catalyzer is 1: 0.25～0.5: 0.01～0.02.
The preparation method of resin base solid-acid material is following: in Erlenmeyer flask, add Resorcinol; With material molar ratio be that the hydroxyethylsulfonic acid of 1:0.5～1 is a bioactive molecule, add with the Resorcinol mass ratio be the water wiring solution-forming of 1:10～20, under agitation condition, drip and the Resorcinol mol ratio is the formaldehyde solution of 1:1～2; Be placed in 70 ℃ of baking ovens behind condensation 30～120h; Obtain red solid, revolve and steam, get the RF resin to doing.The synthetic resin is placed silica tube, under condition of nitrogen gas, under 180 ℃, carry out carbonization condensation 2～10h, wash oven dry again, get the resin base solid acid.
Said waste grease for produce or the catering trade production process in any one or a few of the hogwash fat, sewer oil or the frying oil that obtain.
Said lower aliphatic alcohols is any one of methyl alcohol, ethanol, propyl alcohol, butanols.
Catalyzer after the separation is used for the transesterification reaction of preparation next time biofuel.
A kind of method of resin base solid acid catalysis waste grease biodiesel synthesis is characterized in that:
The preparation of the 1st step, resin base solid acid:
In Erlenmeyer flask, add Resorcinol, with the Resorcinol mol ratio be that the hydroxyethylsulfonic acid of 1:0.5～1 is a bioactive molecule, add then with the Resorcinol mass ratio be the water wiring solution-forming of 1:10～20; Dropping is the formaldehyde solution of 1:1～2 with the Resorcinol mol ratio under agitation condition, places 70 ℃ of baking oven condensations after 30～120 hours, obtains red solid; Revolve and steam to doing; Get the RF resin, resin is placed silica tube, under 180 ℃, carrying out carbonization condensation 2～10 hours under the condition of nitrogen gas; Wash oven dry again, get the resin base solid acid of black solid;
The 2nd step, raw materials pretreatment:
With adding zeyssatite in the waste grease, the zeyssatite consumption is 0.5～2% of a waste grease quality, then under 70 ℃, carries out heated and stirred 1～4 hour, filters, and filtrating is carried out underpressure distillation and removed moisture wherein under 100 ℃;
The 3rd step, transesterification reaction:
Having induction stirring, TM adds grease, lower aliphatic alcohols, catalyzer after step 2 is handled in the 100mL three-necked bottle of reflux condensing tube, and the mass ratio of grease, lower aliphatic alcohols, catalyzer is 1: 0.25～0.5: 0.01～0.02; Heat 70 ℃ of refluxing and stirring about 12 hours;
The 4th step, the separation of catalyzer and the purifying of product:
The thick product that step 3 is made filters, and the catalyzer that leaches directly is used for secondary response down, and filtrating is carried out separatory, tells lower floor's glycerine, and upper strata product adding massfraction is 5～10% NaHCO
3Solution, NaHCO
3Solution usage is 2～6 times of upper strata product quality, and washing to remove unreacted free fatty acids, is used separating funnel to neutral then, tells upper organic phase, with anhydrous MgSO
4Drying removes by filter siccative, and underpressure distillation obtains nearly light yellow transparent product and is biofuel.
The reaction formula that the present invention relates to is following:
。
The present invention compared with prior art has following beneficial effect:
(1) productive rate is high, is 94.7～98.7%;
(2) raw material availability is high, can simultaneously glyceryl ester and free fatty acids be converted into the biofuel product;
(3) catalyst levels is little, accounts for 0.5～3% of reaction raw materials gross weight;
(4) reaction conditions is gentle, and the reaction times is short;
(5) catalyzer is reusable;
(6) there are not side reactions such as saponification;
(7) the waste grease raw materials pretreatment is simple etc.
Below will do further elaboration to the present invention through concrete embodiment.
Embodiment
Embodiment 1: the preparation of biofuel.
The preparation of the 1st step, resin base solid acid:
In Erlenmeyer flask, add Resorcinol, with the Resorcinol mol ratio be that the hydroxyethylsulfonic acid of 1:1 is a bioactive molecule, add then with the Resorcinol mass ratio be the water wiring solution-forming of 1:15; Dropping is the formaldehyde solution of 1:1.2 with the Resorcinol mol ratio under agitation condition, places 70 ℃ of baking oven condensations after 72 hours, obtains red solid; Revolve and steam to doing; Get the RF resin, resin is placed silica tube, under 180 ℃, carrying out carbonization condensation 4 hours under the condition of nitrogen gas; Wash oven dry again, get the resin base solid acid of black solid;
The 2nd step, raw materials pretreatment:
With adding zeyssatite in the waste grease, the zeyssatite consumption is 1% of a waste grease quality, then under 70 ℃, carries out heated and stirred 2 hours, filters, and filtrating is carried out underpressure distillation and removed moisture wherein under 100 ℃;
The 3rd step, transesterification reaction:
Having induction stirring, TM adds grease, lower aliphatic alcohols, catalyzer after step 2 is handled in the 100mL three-necked bottle of reflux condensing tube, and the mass ratio of grease, lower aliphatic alcohols, catalyzer is 1: 0.25: 0.01; Heat 70 ℃ of refluxing and stirring about 12 hours;
The 4th step, the separation of catalyzer and the purifying of product:
The thick product that step 3 is made filters, and the catalyzer that leaches directly is used for secondary response down, and filtrating is carried out separatory, tells lower floor's glycerine, and upper strata product adding massfraction is 5% NaHCO
3Solution, NaHCO
3Solution usage is 5 times of upper strata product quality, and washing to remove unreacted free fatty acids, is used separating funnel to neutral then, tells upper organic phase, with anhydrous MgSO
4Drying removes by filter siccative, and underpressure distillation obtains nearly light yellow transparent product and is biofuel, and productive rate is 98.8%.
Embodiment 2-4:
The preparation method is with embodiment 1, and difference is the bio-oil shown in the employing table 1, and the biodiesel production rate that correspondence makes is following.
Table 1: the biodiesel production rate contrast of different bio-oil preparations.
| Embodiment | Bio-oil | Productive rate/% |
| 2 | Sewer oil | 98.7 |
| 3 | Hogwash fat | 98.6 |
| 4 | Frying oil | 98.9 |
。
Embodiment 5-9
The preparation method is with embodiment 1, and difference is the lower aliphatic alcohols shown in the employing table 1, and the biodiesel production rate that correspondence makes is following.
Table 2: the biodiesel production rate contrast of different lower aliphatic alcohols preparations.
| Embodiment | Lower aliphatic alcohols | Productive rate/% |
| 5 | Ethanol | 98.2 |
| 6 | N-propyl alcohol | 97.4 |
| 7 | Virahol | 96.5 |
| 8 | Propyl carbinol | 93.2 |
| 9 | Isopropylcarbinol | 94.7 |
。
Embodiment 10-14:
The preparation method is with embodiment 1, and difference is that the catalyzer recirculation uses the result that influences to productive rate to see table 3.
Table 3: catalyst recirculation is used the influence to productive rate.
| Embodiment | Catalyzer reuse number of times | Productive rate/% |
| 10 | 0 | 98.7 |
| 11 | 1 | 98.2 |
| 12 | 2 | 97.5 |
| 13 | 3 | 96.8 |
| 14 | 4 | 95.4 |
。
Claims (7)
1. the method for a resin base solid acid catalysis waste grease biodiesel synthesis; It is characterized in that: be raw material with the waste grease; Adopt resin base solid acid as catalyst, carry out transesterification reaction, after reaction finishes with lower aliphatic alcohols; Catalyzer is filtered out from reaction mixture, handle to obtain biofuel through separatory, washing, alkali cleaning, distillation.
2. the method for a kind of resin base solid acid catalysis waste grease biodiesel synthesis according to claim 1 is characterized in that: the mass ratio of said grease, lower aliphatic alcohols, catalyzer is 1: 0.25: 0.01.
3. the method for a kind of resin base solid acid catalysis waste grease biodiesel synthesis according to claim 1 and 2; It is characterized in that: the preparation method of resin base solid-acid material is following: in Erlenmeyer flask, add Resorcinol; With material molar ratio be that the hydroxyethylsulfonic acid of 1:0.5～1 is a bioactive molecule, add with the Resorcinol mass ratio be the water wiring solution-forming of 1:10～20, under agitation condition, drip and the Resorcinol mol ratio is the formaldehyde solution of 1:1～2; Be placed in 70 ℃ of baking ovens behind condensation 30～120h; Obtain red solid, revolve and steam, get the RF resin to doing;
The synthetic resin is placed silica tube, under condition of nitrogen gas, under 180 ℃, carry out carbonization condensation 2～10h, wash oven dry again, get the resin base solid acid.
4. the method for a kind of resin base solid acid catalysis waste grease biodiesel synthesis according to claim 1 is characterized in that: said waste grease for produce or the catering trade production process in any one or a few of the hogwash fat, sewer oil or the frying oil that obtain.
5. the method for a kind of resin base solid acid catalysis waste grease biodiesel synthesis according to claim 1 is characterized in that: said lower aliphatic alcohols is any one of methyl alcohol, ethanol, propyl alcohol, butanols.
6. the method for a kind of resin base solid acid catalysis waste grease biodiesel synthesis according to claim 1 is characterized in that: the catalyzer after the separation is used for the transesterification reaction of preparation next time.
7. the method for a kind of resin base solid acid catalysis waste grease biodiesel synthesis according to claim 1 is characterized in that:
The preparation of the 1st step, resin base solid acid:
In Erlenmeyer flask, add Resorcinol, with the Resorcinol mol ratio be that the hydroxyethylsulfonic acid of 1:0.5～1 is a bioactive molecule, add then with the Resorcinol mass ratio be the water wiring solution-forming of 1:10～20; Dropping is the formaldehyde solution of 1:1～2 with the Resorcinol mol ratio under agitation condition, places 70 ℃ of baking oven condensations after 30～120 hours, obtains red solid; Revolve and steam to doing; Get the RF resin, resin is placed silica tube, under 180 ℃, carrying out carbonization condensation 2～10 hours under the condition of nitrogen gas; Wash oven dry again, get the resin base solid acid of black solid;
The 2nd step, raw materials pretreatment:
With adding zeyssatite in the waste grease, the zeyssatite consumption is 1% of a waste grease quality, then under 70 ℃, carries out heated and stirred 2 hours, filters, and filtrating is carried out underpressure distillation and removed moisture wherein under 100 ℃;
The 3rd step, transesterification reaction:
Having induction stirring, TM adds grease, lower aliphatic alcohols, catalyzer after step 2 is handled in the 100mL three-necked bottle of reflux condensing tube, and the mass ratio of grease, lower aliphatic alcohols, catalyzer is 1: 0.25～0.5: 0.01～0.02; Heat 70 ℃ of refluxing and stirring about 12 hours;
The 4th step, the separation of catalyzer and the purifying of product:
The thick product that step 3 is made filters, and the catalyzer that leaches directly is used for secondary response down, and filtrating is carried out separatory, tells lower floor's glycerine, and upper strata product adding massfraction is 50% NaHCO
3Solution, NaHCO
3Solution usage is 5 times of upper strata product quality, and washing to remove unreacted free fatty acids, is used separating funnel to neutral then, tells upper organic phase, with anhydrous MgSO
4Drying removes by filter siccative, and underpressure distillation obtains nearly light yellow transparent product and is biofuel.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245254A (en) * | 2008-03-28 | 2008-08-20 | 华东师范大学 | Method for producing biological diesel oil with carbon-based solid acid as catalyst |
| CN101249454A (en) * | 2008-03-28 | 2008-08-27 | 华东师范大学 | Solid base catalyst and applications for preparing biological diesel oil |
| CN101250423A (en) * | 2008-03-28 | 2008-08-27 | 华东师范大学 | Method for preparing bio-diesel by using naphthalenesulfonic acid methylal as catalyst |
| CN102070758A (en) * | 2010-12-10 | 2011-05-25 | 绍兴文理学院 | Resorcinol formaldehyde resin base solid acid and preparation method and application thereof |
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- 2012-03-27 CN CN2012100830323A patent/CN102618392A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245254A (en) * | 2008-03-28 | 2008-08-20 | 华东师范大学 | Method for producing biological diesel oil with carbon-based solid acid as catalyst |
| CN101249454A (en) * | 2008-03-28 | 2008-08-27 | 华东师范大学 | Solid base catalyst and applications for preparing biological diesel oil |
| CN101250423A (en) * | 2008-03-28 | 2008-08-27 | 华东师范大学 | Method for preparing bio-diesel by using naphthalenesulfonic acid methylal as catalyst |
| CN102070758A (en) * | 2010-12-10 | 2011-05-25 | 绍兴文理学院 | Resorcinol formaldehyde resin base solid acid and preparation method and application thereof |
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Application publication date: 20120801 |