CN102816645A - Continuous preparation method of biodiesel - Google Patents
Continuous preparation method of biodiesel Download PDFInfo
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- CN102816645A CN102816645A CN2012103111702A CN201210311170A CN102816645A CN 102816645 A CN102816645 A CN 102816645A CN 2012103111702 A CN2012103111702 A CN 2012103111702A CN 201210311170 A CN201210311170 A CN 201210311170A CN 102816645 A CN102816645 A CN 102816645A
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Abstract
The invention relates to a continuous preparation method of biodiesel, which uses waste animal and vegetable grease as the raw material and mainly comprises the following steps: (1) removing impurities and moisture in the raw material; (2) performing continuous esterification reaction in a cation exchange resin fixed bed reactor; (3) separating the esterification product; and (4) performing continuous ester exchange reaction and separation in an anion exchange resin fixed bed reactor. The invention overcomes the problems of severe equipment corrosion, difficult product separation, serious environmental pollution caused by waste acid liquid, failure to realize continuous preparation and the like in the homogeneous catalysis process, is low in cost, high in yield and friendly to environment, and has important market application prospects.
Description
Technical field
The invention belongs to the bioenergy technical field, relate to a kind of biodiesel oil preparing process, particularly a kind of continuous preparation method that utilizes aste vegetable oil and animal fat to prepare biofuel.
Background technology
Along with the continuous aggravation of energy dilemma, the exploitation of new forms of energy has become the focus of various countries' research.And biofuel, i.e. free fatty acids strand alkyl ester is because the substitute that it is renewable, environmental friendliness, wide material sources and advantage such as cheap have become the ideal petrifaction diesel.
At present, the preparation method of biofuel mainly divides physics method and chemical method, and the physics method comprises direct mixing method and microemulsion method; Chemical method comprises high temperature pyrolytic cracking, esterification and ester-interchange method.Wherein, esterification and ester-interchange method comprise (non-) homogeneous acid base catalysis method, enzyme catalysis method and supercritical methanol technology etc. again.But above-mentioned preparation method is accompanied by inevitable shortcoming separately.High-temperature cracking method apparatus expensive for example, reaction is difficult to control; Homogeneous acid base catalysis method catalyzer is difficult for reclaiming, and product is not easily separated, causes equipment corrosion easily, and generation great amount of wastewater etc. is brought problem of environmental pollution; Catalytic efficiency (is low in the heterogeneous acid-base catalysis method of tradition, and catalyzer is difficult for reclaiming, and reaction is difficult to carry out or the like continuously; Enzyme is prone to inactivation in the biological enzyme, and transformation efficiency is low, and speed of reaction is slow; The supercritical methanol method needs high-temperature high-voltage reaction condition or the like.Described these drawbacks limit the widespread use of aforesaid method.
Ion exchange resin provides excellent opportunity for solving the problem that exists among the existing preparation method.Various anion and cation exchange resin have been applied in transesterify and the esterification research, and resin also is fit to continuous operation and industrial-scale production as solid catalyst simultaneously.Therefore adopt ion exchange resin as heterogeneous acid, alkaline catalysts, carry out esterification or transesterification reaction and realize that serialization production will be a kind of trend that will prepare biodiesel technology from now on through filling fixed-bed reactor.[Fuel such as
; 2008; 87 (10-11): 1789-1798] reported that four kinds of Zeo-karbs are used for the useless frying oil of catalytic esterification and prepare fatty ester (being biofuel), but reaction conversion ratio all is lower than 50%.[Fuel Processing Technology such as Liu; 2009; 90 (7-8): 857-862.] the discarded acidifying oil of report D002 Zeo-karb filling fixed bed continuous catalysis esterification preparation biofuel, have the ideal catalytic activity, but the less stable of successive processes; Continuous catalysis esterification 29h, the output of biofuel has been lower than 90%.[Bioresource Technology such as Feng Yaohui; 102 (2011); 3607-3609] reported with NKC-9 catalyzing cation exchange resin oleic acid and methyl alcohol and prepared biofuel; Continuous catalysis esterification 500 hours, transformation efficiency remains at more than 98%, shows higher conversion and ideal operational stability.But this method is only applicable to pure oleic acid raw material, and is not too effective to the complicated material system that contains free fatty acids and glycerin fatty acid ester.
Ke Zhonglu etc. [Ph D dissertation, Zhejiang University] have studied the technology that as catalyzer glycerin fatty acid ester transesterificationization in the deodorization distillate is prepared fatty ester with strong basic ion exchange resin.Keep better 85 ℃ of following catalytic activitys.Under this temperature, in fixed bed, need three transesterification deodorization distillates, just can reach 99.0% transformation efficiency.People such as Edric [Catalysis Today, 174 (1), 2011,54-58] have reported that filling the transesterification reaction that fixed bed is used for theobroma oil and methyl alcohol with anionite-exchange resin prepares biofuel, but the lower transformation efficiency 78% of acquisition.
Although it is more as the report of biodiesel about positive anionite-exchange resin; But because various technology and technology, combine cationic, anionic exchange resin to carry out Technology that esterification and transesterification reaction serialization prepare biofuel and also do not see and invent and application.
The invention provides a kind of is catalyzer with the cationic, anionic exchange resin, is raw material with the aste vegetable oil and animal fat, the method for the serialization preparation through esterification and the integrated realization biofuel of transesterification reaction.In the method for the invention; Produce fatty ester and water through the Zeo-karb continuous catalysis free fatty acids and the esterification of alcohol; Then produce fatty ester and glycerine, prepare fatty ester (being biofuel) thereby can carry out continuous reaction to the complicated raw oil material system that contains free fatty acids and glycerin fatty acid ester through the anionite-exchange resin continuous catalysis glycerin fatty acid ester and the transesterification of alcohol.
Summary of the invention
The object of the present invention is to provide a kind of is catalyzer with the cationic, anionic exchange resin, is raw material with the aste vegetable oil and animal fat, through the continuous preparation method of esterification and the integrated realization biofuel of transesterification reaction.
This method comprises the steps: that mainly (1) remove impurities in raw materials and moisture; (2) in the Zeo-karb fixed-bed reactor, carry out continuous esterification; (3) esterification products separates; (4) in the fixed bed of anion exchange resin reactor drum, carry out the continuous ester interchange reaction and separate.
Used raw material is for example food garbage oil, waste tempura oil, an acidifying wet goods of aste vegetable oil and animal fat; Said aste vegetable oil and animal fat mainly contains free fatty acids and glycerin fatty acid ester; Wherein the free fatty acids weight percentage is approximately 10%～90%, and fatty acid carbons atom number is greatly between 14～22 in free fatty acids and the glycerin fatty acid ester.
Wherein, in the removal of impurity and water of step (1), for example can remove solid impurity, colloid in the raw material, and remove the moisture in the raw material, it is stored in the head tank through for example underpressure distillation through Plate Filtration;
In the continuous esterification of step (2); Add a certain amount of low-carbon (LC) alkanol in the raw material after handling by a certain percentage; And be preheated to homogeneous phase, join in the fixed-bed reactor that are filled with Zeo-karb, under certain reactor drum air speed; Make free fatty acids and low-carbon (LC) alkanol in the raw material carry out esterification, generate free fatty acids lower alkanes alcohol ester and water;
In the esterification products of step (3) separates; Esterification products and unreacted raw material flow out continuously and get into standing demix in the separating tank; Upper materials mainly is the lower alkanes alcoholic solution that contains a small amount of unreacted free fatty acids and product water; The pure and mild free fatty acids of separable recovery lower alkanes after the layering, lower floor's material mainly is esterification products lipid acid lower alkanes alcohol ester and unreacted glycerin fatty acid ester; Lower floor's material is transported in the tundish with charge pump, and the glycerin fatty acid ester in lower floor's material will be as the raw material of step (4) transesterification reaction;
The continuous ester interchange of step (4) reaction with separate; In tundish, add the pure and mild cosolvent of lower alkanes by a certain percentage; And preheating is mixed into homogeneous phase solution, this solution is transported in the fixed-bed reactor that are filled with anionite-exchange resin control reaction temperature with charge pump; Under certain reactor drum air speed, glycerin fatty acid ester and low-carbon (LC) alkanol generation transesterification reaction generate lipid acid lower alkanes alcohol ester and glycerine; The product collection of transesterification reaction in the product jar, is removed the pure and mild cosolvent of lower alkanes through underpressure distillation again, promptly obtain coarse biodiesel, continue the glycerine in the filtering separation coarse biodiesel, can obtain the biofuel product.
Said low-carbon (LC) alkanol is preferably the C1-C4 alkanol, particularly for example methyl alcohol, ethanol or propyl alcohol.
In continuous esterification, employed Zeo-karb is hydrogen type cation exchange resin or becomes hydrogen type cation exchange resin transition through other Zeo-karbs, for example is selected from 001 * 7, a kind of among NKC-9 and the D61.Used resin carries out pre-treatment according to GB GB/T 5476-1996.
In continuous ester interchange reaction, used anionite-exchange resin is the hydroxyl type anion exchange resin or becomes the hydroxyl type anion exchange resin transition through other anionite-exchange resin, for example is selected from 205 * 7, a kind of among D201 and the D26l.Used resin carries out pre-treatment according to GB GB/T 5476-1996.
In continuous esterification, low-carbon (LC) alkanol and aste vegetable oil and animal fat weight ratio be approximately 1: 9～and 1: 1; Be approximately 0.1min～0.25h through charge pump flow rate control reactor drum air speed
-1Esterification reaction temperature is approximately 65～97 ℃.
In the continuous ester interchange reaction, the glycerin fatty acid ester in the lower floor's material after the layering of continuous esterification product is as the continuous ester interchange reaction raw materials.In low-carbon (LC) alkanol of adding and the raw material glycerin fatty acid ester weight ratio be approximately 1: 6～1: 1; The cosolvent of being added is selected from a kind of in MTBE, the trimethyl carbinol, normal hexane and the THF.In cosolvent and the raw material glycerin fatty acid ester weight ratio be approximately 1: 9～1: 2, be approximately 0.1min through charge pump flow rate control reactor drum air speed
-1～0.25h
-1The continuous ester interchange temperature of reaction is approximately 40～50 ℃.
After esterification; The transformation efficiency that free fatty acids is converted into lipid acid lower alkanes alcohol ester adopts the GB/T5530-2005 method to measure the acid number variation according to the hot ethanol method, and the ratio of acid content changing value and raw material acid content is the free fatty acids turnover ratio before and after the reaction.
In transesterification reaction, the transformation efficiency that glycerin fatty acid ester is converted into free fatty acids lower alkanes alcohol ester calculates the fatty acid glycerine ester conversion rate according to the method for thermogravimetric.
According to the method for the invention; After esterification is accomplished; Utilize esterification water byproduct and unreacted free fatty acids to dissolve each other with the low-carbon (LC) alkanol; And with greasy incompatible characteristic, realize separating of residual free lipid acid and product water, the residue grease can directly get into transesterify unit realization transesterification reaction.
Through said continuous esterification and transesterification reaction, free conversion rate of fatty acid can reach more than 98.0% in the esterification, and transesterification reaction can reach more than 95.0%, and biodiesel production rate reaches more than 94.0%.
The resin that is used to fill fixed bed in esterification and the transesterification reaction can adopt online regenerated method to recover catalytic activity; For example at first adopt the online washing resin surface and oil contaminant of low-carbon (LC) alkanol; Then, adopt the online activation of hydrochloric acid alcoholic solution for Zeo-karb; Adopt the online activation of sodium hydroxide alcoholic solution for anionite-exchange resin.
Compared with prior art; The invention has the advantages that through the integrated serialization preparation that has realized biofuel of technology to have avoided that equipment corrosion is serious in the homogeneous catalysis technology, product separates difficult, the spent acid solution environmental pollution is serious and can not realize problem such as serialization generation.This fixed bed potting resin can be realized utilizing through online regeneration again, to practice thrift cost and to reduce labour intensity, has tangible market outlook.
Description of drawings
Fig. 1 prepares the process flow sheet of biofuel according to the method for the invention continuously.
The biofuel thermogravimetric analysis figure of Fig. 2 embodiment of the invention 1.
The product gas chromatogram of Fig. 3 embodiment of the invention 1.
Accompanying drawing mark explanation: 1-head tank; The 2-peristaltic pump; 3-first reactor drum (filling male ion-exchange resin); The 4-water-bath; The 5-separating tank; The 6-tundish; 7-feed supplement jar; 8-second reactor drum (filling anionite-exchange resin); 9-product jar; A: Uniphat A60,10.73%; B: methyl linoleate 50.42%; C: Witconol 2301,35.26%; D: methyl stearate, 3.60%.
Embodiment
Further exemplarily specify the present invention below in conjunction with specific embodiment.
Embodiment 1
Used process flow sheet is shown in accompanying drawing 1.Under 50 ℃, at first remove solid impurity, colloid in the raw material food garbage oil, remove moisture in the raw material through underpressure distillation 30min then, it is stored in the head tank 1 through Plate Filtration.The free fatty acid content of removal of impurities of learning from else's experience is 10% food garbage oil 900 grams, to wherein adding methyl alcohol 100 grams, stirs, and is preheating to 65 ℃; Reactant is joined in first fixed-bed reactor 3 of Zeo-karb (001 * 7) through charge pump, using circulator bath to keep temperature of charge is 65 ℃, and conditioned reaction device air speed is 0.25h
-1, let free lipid acid and methyl alcohol carry out esterification in the food garbage oil, obtain fatty acid methyl ester and water.Effusive product collection standing demix in the separating tank 5.Separating tank 5 is the mixtures such as water of methyl alcohol, unreacted free fatty acids and generation at the middle and upper levels, separates recyclable methyl alcohol in back and free fatty acids.Lower floor is glycerin fatty acid ester and fatty acid methyl ester admixture, adds as the transesterification reaction raw material to be stored in the tundish 6.
Then in tundish 6, add 810 gram methyl alcohol and 90 gram cosolvent THFs, and be heated to 50 ℃.Then reactant is joined in second fixed-bed reactor 8 of anionite-exchange resin (D201) through charge pump, using circulator bath controlling reactor temperature is 50 ℃ of temperature, and the reactor drum air speed is 0.25h
-1, let glycerin fatty acid ester and methyl alcohol carry out transesterification reaction, change into fatty acid methyl ester and glycerine.Effusive product collection in product jar 9, is removed methyl alcohol and THF through underpressure distillation at last, obtain coarse biodiesel.
In the present embodiment, the free fatty acids transformation efficiency through acid base titration is 99.2%, and obtaining glycerin fatty acid ester fat transformation efficiency through thermogravimetry is 95.5%, and biodiesel production rate is 94.7%, shown in accompanying drawing 2.The glycerine that continues in the crude biofuel obtains the biofuel product, and its composition mainly contains Uniphat A60, methyl stearate, Witconol 2301, methyl linoleate, shown in accompanying drawing 3.
Embodiment 2
Used process flow sheet is shown in accompanying drawing 1.The free fatty acid content of removal of impurities of learning from else's experience is 50% waste tempura oil 1200 grams, to wherein adding ethanol 600 grams, stirs, and is preheating to 78 ℃; Reactant is joined in first fixed-bed reactor 3 of Zeo-karb (NKC-9) through charge pump, using circulator bath to keep temperature of charge is 78 ℃, and conditioned reaction device air speed is 0.1min
-1, let free lipid acid and ethanol carry out esterification in the waste tempura oil, obtain fatty-acid ethyl ester and water.Effusive product collection standing demix in the separating tank 6.Separating tank 6 upper stratas are the mixtures such as water of ethanol, unreacted free fatty acids and generation, separate recyclable ethanol in back and free fatty acids.Lower floor is glycerin fatty acid ester and fatty-acid ethyl ester mixture, as the transesterification reaction raw material storage in tundish 6.
Then in tundish 6, add 100 gram ethanol and 300 gram cosolvent normal hexanes, and be heated to 40 ℃.Then reactant is joined in second fixed-bed reactor 8 of anionite-exchange resin (205 * 7) through charge pump, using circulator bath controlling reactor temperature is 40 ℃ of temperature, and the reactor drum air speed is 0.1min
-1, let glycerin fatty acid ester and ethanol carry out transesterification reaction, change into fatty-acid ethyl ester and glycerine.Effusive product collection in product jar 9, is removed ethanol and normal hexane through underpressure distillation at last, obtain coarse biodiesel.Measuring method is shown in embodiment 1, and recording the free fatty acids transformation efficiency is 98.7%, and the fatty acid glycerine ester conversion rate is 95.8%, and biodiesel production rate is 94.6%.
Embodiment 3
Used process flow sheet is shown in accompanying drawing 1.The free fatty acid content of removal of impurities of learning from else's experience is 90% acidifying oil 1000 grams, to wherein adding propyl alcohol 500 grams, stirs, and is preheating to 97 ℃; Reactant is joined in first fixed-bed reactor 3 of Zeo-karb (D61) through charge pump, using circulator bath to keep temperature of charge is 97 ℃, and conditioned reaction device air speed is 0.08min
-1, let free lipid acid and propyl alcohol carry out esterification in the acidifying oil, obtain lipid acid propyl ester and water.Effusive product collection standing demix in the separating tank 6.Separating tank 6 is the mixtures such as water of propyl alcohol, unreacted free fatty acids and generation at the middle and upper levels, separates recyclable propyl alcohol in back and free fatty acids.Lower floor is glycerin fatty acid ester and lipid acid propyl ester mixture, adds as the transesterification reaction raw material to be stored in the tundish 6.
Then in tundish 6, add the 50 gram propyl alcohol and the 30 gram cosolvent trimethyl carbinols, and be heated to 50 ℃.Then reactant is joined in second fixed-bed reactor 8 of anionite-exchange resin (D261) through charge pump, using circulator bath controlling reactor temperature is 50 ℃ of temperature, and the reactor drum air speed is 0.08min
-1, let glycerin fatty acid ester and propyl alcohol carry out transesterification reaction, change into lipid acid propyl ester and glycerine.Effusive product collection in product jar 9, is removed the propyl alcohol and the trimethyl carbinol through underpressure distillation at last, obtain coarse biodiesel.Measuring method such as embodiment 1 are said, and recording the free fatty acids transformation efficiency is 98.2%, and the fatty acid glycerine ester conversion rate is 96.5%, and biodiesel production rate is 94.8%.
Said embodiment can make those skilled in the art more comprehensively understand the present invention, but does not limit the present invention in any way, and any variation and change in spirit of the present invention all falls into scope of the present invention.
Claims (10)
1. a biofuel continuous preparation method is a raw material with the aste vegetable oil and animal fat, comprises the steps: that mainly (1) remove impurities in raw materials and moisture; (2) in the Zeo-karb fixed-bed reactor, carry out continuous esterification; (3) esterification products separates; (4) in the fixed bed of anion exchange resin reactor drum, carry out the continuous ester interchange reaction and separate.
2. preparation method as claimed in claim 1 is wherein in the impurity removing matter and moisture of step (1): remove by filter solid impurity, colloid in the raw material, and remove moisture wherein through underpressure distillation;
In the continuous esterification of step (2): add a certain amount of low-carbon (LC) alkanol in the raw material after handling by a certain percentage; And be preheated to homogeneous phase; Join in the fixed-bed reactor that are filled with Zeo-karb; Under certain reactor drum air speed, free lipid acid and low-carbon (LC) alkanol carry out esterification in the raw material, generate free fatty acids lower alkanes alcohol ester and water;
In the esterification products of step (3) separated: esterification products and unreacted raw material flowed out continuously and get into standing demix in the separating tank, tell upper materials, reclaim the pure and mild free fatty acids of corresponding lower alkanes, and lower floor's mass transport is in tundish;
The continuous ester interchange of step (4) reaction with separate: in tundish, add the pure and mild cosolvent of lower alkanes by a certain percentage; And preheating is mixed into homogeneous phase solution; This solution is transported to charge pump in the fixed-bed reactor that are filled with anionite-exchange resin, and control reaction temperature is under certain reactor drum air speed; Glycerin fatty acid ester and low-carbon (LC) alkanol carry out transesterification reaction, generate lipid acid lower alkanes alcohol ester and glycerine; Remove the pure and mild cosolvent of lower alkanes in the reaction product through underpressure distillation, promptly obtain coarse biodiesel, the glycerine that continues in the crude biofuel obtains the biofuel product.
3. preparation method according to claim 1 and 2, wherein used aste vegetable oil and animal fat mainly contains free fatty acids and glycerin fatty acid ester, and wherein the free fatty acids weight percentage is 10%～90%.
4. preparation method according to claim 1 and 2; Wherein in said continuous esterification; Employed Zeo-karb is hydrogen type cation exchange resin or becomes hydrogen type cation exchange resin transition through other resin cation(R.C.)s, and said Zeo-karb for example is selected from 001 * 7, a kind of among NKC-9 and the D61.
5. preparation method according to claim 1 and 2; Wherein in described continuous ester interchange reaction; Used anionite-exchange resin is the hydroxyl type anion exchange resin or becomes the hydroxyl type anion exchange resin transition through other anionite-exchange resin, and said anionite-exchange resin for example is selected from 205 * 7, a kind of among D201 and the D261.
6. preparation method according to claim 2, wherein in said continuous esterification, low-carbon (LC) alkanol and raw material aste vegetable oil and animal fat weight ratio are 1: 9～1: 1; Material reaction device air speed is 0.1min-1～0.25h-1; Esterification reaction temperature is 65～97 ℃.
7. preparation method according to claim 2, wherein in described continuous ester interchange reaction, the glycerin fatty acid ester weight ratio is 1: 6～1: 1 in low-carbon (LC) alkanol amount of adding and the raw material.
8. preparation method according to claim 2, wherein said low-carbon (LC) alkanol is C1-C4 alkanol, particularly methyl alcohol, ethanol or propyl alcohol.
9. preparation method according to claim 2; Wherein in described continuous ester interchange reaction; Added cosolvent is selected from a kind of in MTBE, the trimethyl carbinol, normal hexane and the THF, and the glycerin fatty acid ester weight ratio is 1: 9～1: 2 in said cosolvent and the raw oil.
10. preparation method according to claim 2, wherein in the continuous ester interchange reaction, the reactor drum air speed is 0.1min
-1～0.25h
-1, described continuous ester interchange temperature of reaction is 40～50 ℃.
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| CN105713733A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Pre-esterification method for preparation of biodiesel |
| CN108219982A (en) * | 2016-12-22 | 2018-06-29 | 内蒙古中细软技术开发有限公司 | Novel cosolvent method biodiesel synthesis |
| CN113583724A (en) * | 2020-04-30 | 2021-11-02 | 河南工程学院 | Efficient green continuous preparation method of biodiesel |
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| CN113583724A (en) * | 2020-04-30 | 2021-11-02 | 河南工程学院 | Efficient green continuous preparation method of biodiesel |
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