CN105062697A - Method for improving yield of biodiesel prepared through kitchen grease enzymic method through pretreatment - Google Patents
Method for improving yield of biodiesel prepared through kitchen grease enzymic method through pretreatment Download PDFInfo
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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
- 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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
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Abstract
The invention belongs to the technical field of kitchen waste treatment and particularly discloses a method for improving the yield of biodiesel prepared through a kitchen grease enzymic method through pretreatment. The method includes the following steps that firstly, impurities in kitchen waste are removed, and microwave treatment, ultrasonic wave treatment and hydro-thermal treatment is conducted on the kitchen waste in sequence; secondly, three-phase separation is conducted, and upper-layer grease is obtained; thirdly, oxidation is conducted by leading ozone in; fourthly, immobilized composite lipase is added into grease obtained in the third step, and short chain alcohol is added for conducting a transesterification reaction to prepare the biodiesel, wherein the immobilized composite lipase in the forth step comprises geotrichum candidum lipase, candida lipase and burkholderia cepacia lipase. According to the method, microwave treatment, ultrasonic wave treatment and hydro-thermal treatment are combined for treating kitchen waste, the kitchen grease precipitated amount is increased by 10-50 % than that before treatment and is increased by 2-30% than that obtained by adopting single pretreatment, the kitchen grease precipitated amount is effectively increased, and the productivity and the yield of the biodiesel prepared through the enzymic method are obviously improved.
Description
Technical field
The invention belongs to changing food waste processing technology field, be specifically related to a kind of method utilizing pre-treatment to improve meal kitchen grease process for preparing biodiesel by enzyme output, particularly relate to a kind of method utilizing microwave and ultrasound and hydrothermal treatment consists to improve meal kitchen grease process for preparing biodiesel by enzyme output.
Background technology
Meal kitchen preparing biodiesel from lipid utilizes animal-plant oil etc. as raw material, through a kind of renewable energy source that reaction modifying generates, can replace or Some substitute petroleum diesel.In order to improve biodiesel production rate and output, for methyl alcohol and animal-plant oil mutual solubility poor, reaction system is two-phase, and transesterification reaction is only carried out at interface, the problems such as speed of reaction is low, research emphasis is progressively placed on by people increases phase interface area, improve catalyzer effective concentration aspect.
Ultrasonic wave and microwave are the technology of two kinds of conventional auxiliary biodiesel synthesis respectively.Ultrasonic wave is a kind of elastic mechanical ripple in material medium; Microwave is a kind of frequency is 300MHz ~ 300GHz, and wavelength is the frequency electromagnetic waves of 0.001 ~ 1m.Utilize ultrasonic wave, microwave-assisted to accelerate chemical reaction, obtain higher productive rate in the short period of time.Utilize ultrasonic wave and Microwave-assisted synthesis biodiesel technology to be placed in by grease in ultrasonic wave and microwave field mostly in prior art, under the effect of chemical catalyst, carry out transesterification reaction with methyl alcohol.
In addition, hydrothermal treatment consists is a kind of novel effective pretreatment process, and it is heating changing food waste being had to control in aqueous environment, improves the physical and chemical process of rubbish stuctures and properties, is conducive to the separation of waste oil, recycle and reuse.Patent ZL201410000823.4 discloses a kind of method of changing food waste production biofuel, the method isolates grease from the changing food waste after hydrothermal treatment consists, recycling compound lipases carries out the transesterification reaction of efficient catalytic meal kitchen grease, the grease amount of precipitation of every 1000g changing food waste is up to 182g, and its yield of biodiesel reaches 178g.Although the biofuel maximum output of this invention reaches 98.3%(v/v), because the grease amount of precipitation of its unit weight changing food waste is lower, the output of its biofuel is still lower.
Have in prior art and adopt microwave or/and ultrasonic wave prepares the technology of biofuel, the method is placed in ultrasonic wave and microwave field by grease to carry out chemical catalysis transesterification reaction; And the present invention is before transesterification, adopt microwave, ultrasonic wave and hydro-thermal combined pretreatment changing food waste, improve the grease amount of precipitation of changing food waste, then the grease of precipitation is carried out transesterification reaction, combined pretreatment can effectively improve its biodiesel production rate and output.
The major cause obtaining above beneficial effect is: the waste of energy of microwave action in changing food waste inside can direct heating changing food waste, and increase can oil slick amount of precipitation; Significantly improve the catalysis directional property of changing food waste cracking simultaneously, make meal kitchen grease be cracked into short chain molecule by long-chain, promote transesterification reaction.Ultrasonic wave to changing food waste the effect that rises be mainly cavatition, acutely interact between particulate, the mechanical effect of generation can facilitate the emulsification of liquid and the dispersion of solid.In addition, because ultrasonic frequency is high, energy is large, can be produced significant heat effect, the temperature of changing food waste can be made suddenly to raise, serve good stirring action by during Absorption of Medium, promotes the precipitation of meal kitchen grease; In addition, ultrasonic wave also has chemical effect, can impel and occurs or accelerate some chemical reaction, and accelerate hydrolysis, the decomposition and aggregation process of many chemical substances.Under ul-trasonic irradiation, C-C bond rupture in the grease molecules of meal kitchen, macromolecular hydrocarbons decompose is micromolecular hydrocarbon polymer, is beneficial to transesterification reaction.And hydrothermal treatment consists changing food waste is carried out thermochemical treatment under the environment having water, phase behavior, rate of diffusion and solvation effect can be changed, increase spread coefficient, reduce mass transfer, heat transmission resistance, thus be conducive to diffusion and control phase separation, Reaction time shorten.
Visible, changing food waste is carried out microwave, ultrasonic wave and hydrothermal treatment consists, the increase of yield of biodiesel can be realized.Above-mentioned three kinds of modes are carried out combination comparison by contriver, and discovery is when carrying out microwave, ultrasonic wave and hydrothermal treatment consists successively, and changing food waste can oil slick amount increase at most, and biodiesel production rate is also improved simultaneously.Therefore the present invention adopts microwave, ultrasonic wave and hydrothermal treatment consists to carry out the pretreated mode of changing food waste successively.
Changing food waste through combined pretreatment is carried out three phase separation and obtain meal kitchen grease, pass into ozone to meal kitchen grease to be oxidized, realize decolouring and removing the impurity, stink, protein etc. in grease, eliminate the conventional operation such as water-washing desalting, filtering and impurity removing, active carbon purifying, make production technique simpler, and the generation of decreasing pollution thing.In addition, ozone is a kind of strong oxidizer, can decompose gas chromatography, and destroys the biological structure of bacterium, virus and other microorganism within a short period of time, makes it to lose viability, is beneficial to the catalysis of follow-up lipase, improves biodiesel production rate.
Meal kitchen grease through ozone oxidation carries out next step transesterification.The present invention is thinking after a large amount of experimental studies, utilizes geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase to make immobilization compound lipases, can the transesterification reaction of effectively catalysis grease and short chain alcohol.Wherein, the lipase that Geotrichum produces has stronger specificity, only acts on the ester bond that oleic acid is formed; The lipase that candiyeast produces only acts on 1 or 3 ester bond; And Burkholderia cepacia lipase has better resistance to multiple organic solvent (alcohol), heat, oxygenant, tensio-active agent, stain remover, proteolytic enzyme etc., be one of lipase be most widely used in nonaqueous phase catalysis at present.By three's compound, effectively transesterification reaction can be carried out by catalysis meal kitchen grease.
Preferably, S4 is that the grease that obtained by S3 flows into and is equipped with in one or more levels enzyme reactor of immobilization compound lipases, adds short chain alcohol and carries out transesterification reaction and prepare biofuel.
Preferably, immobilization compound lipases described in S4 is made up of geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase 1 ~ 10:1 in mass ratio ~ 10:5 ~ 25.By above-mentioned three kinds of enzymes in proportion scope composite after make immobilization compound lipases, can play each enzyme synergy, promote mutually, gained biodiesel production rate is high compared with lipase composite outside ratio by 10 ~ 25%.
Preferably, passing into ozone to S3 makes the concentration of ozone in grease be 15 ~ 20g/L.More preferably, the flow velocity passing into ozone in S3 is 7 ~ 10L/min, and the time is 2 ~ 30min.
Preferably, add in the grease that S3 obtains after compound lipases is hydrolyzed and carry out S4 step again, described compound lipases comprises geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase.Adopt compound lipases to be longer chain fatty acid and glycerine by the triglyceride hydrolysis in the grease of meal kitchen, make follow-up transesterification reaction more efficient.By composite in described ratio for above-mentioned three kinds of enzymes, can give full play to the effect of each enzyme, mutually work in coordination with, acting in conjunction, fat hydrolysis is effective.
Preferably, compound lipases described in S3 is made up of geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase 0.2 ~ 6:1 in mass ratio ~ 10:1.5 ~ 15.By composite for three kinds of enzymes within aforementioned proportion scope, each enzyme maximum effect can be played.Carry out composite outside this ratio, fat hydrolysis effect declines, and biodiesel production rate reduces 5 ~ 15%.
Preferably, the compound lipases for being hydrolyzed described in S3 accounts for 0.5 ~ 10% of grease weight, and hydrolysis time is 0.5 ~ 10h, and hydrolysis temperature is 25 ~ 45 DEG C.Preferably, the speed of shaking during described hydrolysis is 120 ~ 220rpm/min.
Preferably, the power of microwave described in S1 is 100w ~ 2500kw, and the time is 2 ~ 120min, and temperature is 90 ~ 250 DEG C.
Preferably, hyperacoustic power described in S1 is 15 ~ 1500w/L, and the treatment time is 5 ~ 60min.
Preferably, the temperature of hydrothermal treatment consists described in S1 is 90 ~ 250 DEG C, and the treatment time is 5 ~ 150min.
Process described in S1 and carry out in the integration apparatus that microwave generator, ultrasonic generator and hydrothermal device are housed, or carry out successively in microwave reactor, ultrasound reactor and hydrothermal reactor respectively.
Preferably, three phase separation described in S2 is left standstill by changing food waste, then isolate upper strata grease.More preferably, three phase separation described in S2 is that standing separation goes out upper strata grease by changing food waste with after spraying quick-fried mode and discharging.Spraying quick-fried mode makes grease farthest be separated with solid, water, and increase can oil slick amount of precipitation.
Preferably, immobilization compound lipases described in S4 accounts for 0.5 ~ 35% of meal kitchen grease weight.
Preferably, the carrier in immobilization compound lipases described in S4 is made up of agriculture and forestry organic waste material that pulverizing.Preferably, described carrier powder is broken to 0.5 ~ 10cm.More preferably, described agriculture and forestry organic waste material comprises one or more in stalk, rice husk, scrap stock, fuel wood, bark, Pericarppium arachidis hypogaeae, branch bavin, volume skin or wood shavings.Adopt agriculture and forestry organic waste material as carrier, not only can turn waste into wealth, and due to agriculture and forestry organic waste material be crude substance, be conducive to fatty enzyme immobilizatio.When carrier cannot use, preferably, fermentable is carried out to realize its recycling after being collected by described carrier.
Preferably, in immobilization compound lipases described in S4, the mass ratio of compound lipases and carrier is 0.5:1 ~ 30.
Preferably, a kind of method utilizing pre-treatment to improve meal kitchen grease process for preparing biodiesel by enzyme output, comprises the steps:
S1. remove the foreign material in changing food waste, changing food waste is carried out microwave, ultrasonic wave and hydrothermal treatment consists successively;
S2. by the changing food waste three phase separation through S1 process, obtaining upper strata can oil slick fat;
S3. pass into ozone in the grease obtained to S2 to be oxidized; In the grease after oxide treatment, add compound lipases be hydrolyzed; Grease after hydrolysis treatment realizes dehydration through molecular sieve or silica gel;
S4. flow in grease S3 obtained and be equipped with in one or more levels enzyme reactor of immobilization compound lipases, add short chain alcohol and carry out transesterification reaction and prepare biofuel;
Wherein, immobilization compound lipases described in compound lipases described in S3 and S4 includes geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase.
Preferably, described short chain alcohol is one or more in methyl alcohol, ethanol, propyl alcohol or butanols.
Preferably, the molar mass ratio of described short chain alcohol and grease is 5 ~ 50:1.
Preferably, the feed postition of described short chain alcohol is that equal uniform flow adds or point more than 3 times batches of interpolations.
Preferably, S4 adds solubility promoter when transesterification reaction.More preferably, described solubility promoter is sherwood oil.
Preferably, described solubility promoter add-on is 0.2 ~ 1.5% of oil quality.
Preferably, the temperature of described transesterification reaction is 30 ~ 60 DEG C, and shaking speed is 140 ~ 250rpm/min, and the reaction times is 4 ~ 72h.
Preferably, stratification after meal kitchen grease completes S4 transesterification reaction, upper strata is rough biofuel, and lower floor is glycerine; Then, rough biofuel is filtered, obtain refining biodiesel and reclaim solid catalyst.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention adopts microwave, ultrasonic wave and hydrothermal technique to process changing food waste successively, meal kitchen grease amount of precipitation increases by 10 ~ 50% than before process, than adopting, the meal kitchen grease amount of precipitation of individual event preconditioning technique is high by 2 ~ 30%, effective increase meal kitchen grease amount of precipitation, and improve productive rate and the output of process for preparing biodiesel by enzyme.
(2) the present invention adopts ozone oxidation through the meal kitchen grease of microwave, ultrasonic wave and hydrothermal pretreatment, removes impurity, stink, protein etc. in grease; Save the pretreatment procedures such as water-washing desalting, filtering and impurity removing, active carbon purifying, make production technique simpler, convenient, effectively can improve the preparation working efficiency of biofuel and the generation of decreasing pollution thing.
(3) the present invention adopts compound lipases to be longer chain fatty acid and glycerine by the triglyceride hydrolysis in the grease of meal kitchen, makes follow-up transesterification reaction more efficient.
(4) the present invention utilizes immobilization compound lipases as catalyst transesterification reaction, and biodiesel production rate can reach 99%, and immobilization compound lipases easily reclaims, can repeatedly use.
(5) the present invention is when preparing refining biodiesel without the need to distillation, and save mass energy, production cost is low.Biodiesel fuel quality meets country's " diesel-fuel blending biofuel (BD100) " (GB/T20828-2007) requirement.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method utilizing pre-treatment to improve meal kitchen grease process for preparing biodiesel by enzyme output.Described method adopts microwave, ultrasonic wave and hydrothermal treatment consists combination treatment changing food waste, meal kitchen grease amount of precipitation increases by 10 ~ 50% than before process, than adopting individual event pre-treatment to increase by 2 ~ 30%, effectively increasing meal kitchen grease amount of precipitation, improving productive rate and the output of process for preparing biodiesel by enzyme.
Above-mentioned purpose of the present invention is achieved by the following technical programs.
Utilize pre-treatment to improve a method for meal kitchen grease process for preparing biodiesel by enzyme output, comprise the steps:
S1. remove the foreign material in changing food waste, changing food waste is carried out microwave, ultrasonic wave and hydrothermal treatment consists successively;
S2. by the changing food waste three phase separation through S1 process, upper strata grease is obtained;
S3. pass into ozone in the grease obtained to S2 to be oxidized;
S4. add immobilization compound lipases in the grease obtained to S3, and add short chain alcohol and carry out transesterification reaction and prepare biofuel;
Wherein, immobilization compound lipases described in S4 comprises geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase.
Accompanying drawing explanation
Fig. 1 is that the present invention utilizes pre-treatment to improve the process flow sheet of the method for meal kitchen grease process for preparing biodiesel by enzyme output.
Embodiment
Below in conjunction with Figure of description and specific embodiment, the present invention is described in further details, but embodiment does not limit in any form the present invention.Unless stated otherwise, the present invention adopts reagent, method and apparatus are the art conventional reagent, method and apparatus.
embodiment 1
Utilize pre-treatment to improve a method for meal kitchen grease process for preparing biodiesel by enzyme output, comprise the steps:
S1. remove the foreign material such as chopsticks, plastics bag in changing food waste, changing food waste is carried out successively microwave, ultrasonic wave and hydrothermal treatment consists; The power of described microwave is 1000kw, and make meal kitchen grease temperature maintain 110 DEG C, the treatment time is 20min; Described hyperacoustic power is 800w/L, and the treatment time is 15min; Hydrothermal treatment consists temperature is 180 DEG C, and the treatment time is 90min; Above-mentioned process is carried out in the integration apparatus that microwave generator, ultrasonic generator and hydrothermal device are housed.
S2. by quick-fried in another container for the changing food waste spray through S1 process, leave standstill and make its three phase separation, swim state grease on collection upper strata.
S3. in the meal kitchen grease obtained, pass into ozone, make ozone concn be 15g/L, ozone flow velocity is 10L/min, and the time of passing into is 10min;
1g compound lipases is added, 30 DEG C, 180rpm/min is hydrolyzed 3h in the 100g through ozonize eats kitchen grease; Described compound lipases by geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase in mass ratio 1:5:10 form;
Kitchen grease of eating through the 100g of peroxidation and hydrolysis is flowed into transesterification reactor after molecular sieve dehydration.
S4. be filled with 10g immobilization compound lipases in described transesterification reactor, add 15g methyl alcohol (10.35mmol) and 1g sherwood oil, 45 DEG C, carry out transesterification reaction under 200rmp/min condition; After this, within every 12 hours, add equivalent 15g methyl alcohol (10.35mmol), until reaction 48h stops;
Wherein, immobilization compound lipases described in S4 by geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase in mass ratio 5:5:8 be fixed on and be ground on 2cm branch bavin; Wherein, the mass ratio of three kinds of enzymes and branch bavin is 1:9.
S5. by reacted for S4 liquid input separatory equipment stratification, upper strata is rough biofuel, and lower floor is glycerine, and be separated two kinds of liquid and obtain rough biofuel, rough biofuel obtains refining biodiesel after activated carbon filtration.
That prepares biofuel by above-mentioned steps the results are shown in Table 1.
embodiment 2
The step that the present embodiment prepares biofuel is basic identical with embodiment 1, difference is the mass ratio of geotrichum candidum lipase, lipase from candida sp and each enzyme of Burkholderia cepacia lipase in immobilization compound lipases described in compound lipases described in S3 and S4, being 0.2:10:1.5 in step S3, is 1:1:25 in step S4.
That prepares biofuel by above-mentioned steps the results are shown in Table 1.
embodiment 3
The step that the present embodiment prepares biofuel is basic identical with embodiment 1, difference is: 1. three phase separation described in step S2 unloads to be depressed into normal pressure, changing food waste is delivered to triphase separator, obtains meal kitchen grease after leaving standstill, and do not adopt spray quick-fried mode changing food waste to be delivered to another container; The mass ratio of geotrichum candidum lipase, lipase from candida sp and each enzyme of Burkholderia cepacia lipase 2. in immobilization compound lipases described in compound lipases described in S3 and S4, being 6:1:15 in step S3, is 10:10:5 in step S4.
That prepares biofuel by above-mentioned steps the results are shown in Table 1.
comparative example 1
The step that this comparative example prepares biofuel is basic identical with embodiment 1, and difference is that S1 takes individual event pretreatment mode: 1. process only adopts Microwave Pretreatment changing food waste; 2. process only adopts ultrasonic pretreatment changing food waste; 3. process only adopts hydrothermal pretreatment changing food waste.
That prepares biofuel by above-mentioned each processing mode the results are shown in Table 1, knownly oil slick amount of precipitation can reduce 15.7 ~ 30.1% than embodiment, and biodiesel production rate also reduces to some extent, but it is little to reduce degree of convergence.Reason may be, three kinds of pre-treatment combined action are more conducive to being separated of liquid and solid, can oil slick amount of precipitation the highest; Being used alone above-mentioned pretreatment mode all can make meal kitchen grease be cracked into short chain molecule by long-chain to a certain extent, but far below three kinds of pretreated synergies, each embodiment of transesterification efficiency ratio is low.
comparative example 2
The step that this comparative example prepares biofuel is basic identical with embodiment 1, and difference is step S1 or/and S4 takes following several processing mode: process 1. S1 and changing food waste is carried out microwave and hydrothermal treatment consists successively, do not adopt ultrasonication; Process 2. S1 and changing food waste is carried out ultrasonic wave and hydrothermal treatment consists successively, do not adopt microwave treatment; Process 3. S1 and changing food waste is carried out microwave and ultrasound process successively, do not adopt hydrothermal treatment consists; Process 4. S1 and changing food waste is carried out hydro-thermal, microwave and ultrasound process successively; Process 5. S1 only hydrothermal treatment consists changing food waste, in S4, the grease obtained is placed in ultrasonic wave and microwave field, under the effect of chemical catalyst sodium methylate, carry out transesterification reaction with methyl alcohol, wherein above-mentioned ultrasonic wave is identical with microwave condition with ultrasonic wave corresponding in S1 step in embodiment 1 with the condition of microwave; Process and 6. do not carry out ultrasonic wave, microwave and hydrothermal treatment consists changing food waste in S1, be directly separated the grease in changing food waste after sorting in step 1.
That prepares biofuel by above-mentioned each processing mode the results are shown in Table 1.
1. process lacks ultrasonication in the middle of microwave and hydrothermal treatment consists.Hyperacoustic cavatition, heat effect and chemical effect do not impact changing food waste, and cause meal kitchen grease amount of precipitation to reduce than embodiment 1, biodiesel production rate reduces 6.7% simultaneously.2. process lacks microwave treatment before ultrasonic wave and hydrothermal treatment consists, and the heating of microwave, the catalysis directive action of cracking do not impact changing food waste; Meal kitchen grease amount of precipitation, biodiesel production rate are not only few than embodiment 1, and 1. lower than process, and the impact of visible microwave on follow-up grease precipitation and transesterification is larger than ultrasonic wave.3. process lacks hydrothermal treatment consists after microwave, ultrasonication, and the thermochemistry effect of hydrothermal treatment consists does not impact changing food waste; Meal kitchen grease amount of precipitation, biodiesel production rate than embodiment 1 and process 1. low, but 2. higher than process, visible hydrothermal treatment consists follow-up grease is separated out and the impact of transesterification larger than ultrasonic wave, less than microwave.Process is 4. after change three kinds of pre-treatment sequence, and meal kitchen grease amount of precipitation, biodiesel production rate all reduce than embodiment 1, and biodiesel production rate is 1. lower than process, shows that the change of three kinds of pre-treatment sequence can affect greatly the productive rate of biofuel.5. process utilizes hydrothermal pretreatment changing food waste, and meal kitchen grease amount of precipitation is 6. higher than control treatment; Chemical method is adopted to carry out esterification in ultrasonic wave and microwave field precipitation grease, biodiesel production rate is 6. only higher by 1% than control treatment, and than process 1. ~ 4. low, though show that hydrothermal treatment consists can increase meal kitchen grease amount of precipitation, but it is not obvious to prepare biodiesel production rate impact to alkaline process, and pre-treatment is larger to process for preparing biodiesel by enzyme yield impact.
comparative example 3
The step that this comparative example prepares biofuel is basic identical with embodiment 1, and difference is that the lipase single fat enzyme in S3 and S4 replaces, specific as follows: process 1. in S3 and S4 with single geotrichum candidum lipase replacement compound lipases; Process and 2. replace compound lipases with single lipase from candida sp in S3 and S4; Process and 3. replace compound lipases with single Burkholderia cepacia lipase in S3 and S4.
That prepares biofuel by above-mentioned each processing mode the results are shown in Table 1.As shown in Table 1, replace artifact diesel yield to decline obviously compound lipases single fat enzyme, show that the synergy of compound lipases can improve biodiesel production rate effectively.
comparative example 4
The step that this comparative example prepares biofuel is basic identical with embodiment 1, distinguishes and is that the composition of immobilization compound lipases described in S4 takes following several processing mode: process 1. lipase from Aspergillus Niger, fold candida and klebsiella in mass ratio 5:5:8 add; Process 2. lipase from Aspergillus Niger and klebsiella in mass ratio 5:8 add; Process 3. lipase from Aspergillus Niger: geotrichum candidum lipase: candida rugosa lipase: Burkholderia cepacia lipase in mass ratio 7:8:6:15 adds.
That prepares biofuel by above-mentioned each processing mode the results are shown in Table 1.Result shows, it is lower that the compound lipases including other enzyme limits catalytic capability in proportional range in the present invention, and biodiesel production rate is lower.
comparative example 5
The step that this comparative example prepares biofuel is basic identical with embodiment 1, and difference is that described in S4, each enzyme of immobilization compound lipases adopts following ratio: process 1. 0.5:8:25; Process 2. 7:15:10; Process 3. 2:3:3
That prepares biofuel by above-mentioned each processing mode the results are shown in Table 1.Result shows, exceeding the present invention, to limit the composite lipase-catalyzed ability obtained of proportional range lower, and biodiesel production rate is lower.
comparative example 6
The step that this comparative example prepares biofuel is basic identical with embodiment 1, distinguishes and is not adopt ozonize changing food waste in step S3, and what it prepared biofuel the results are shown in Table 1.
Result shows, the productive rate of ozone to process for preparing biodiesel by enzyme is improved effect.
comparative example 7
The step that this comparative example prepares biofuel is basic identical with embodiment 1, distinguishes and is not adopt compound fat enzymic hydrolysis changing food waste in S3, and what it prepared biofuel the results are shown in Table 1.
Result shows, the productive rate of hydrolysis to process for preparing biodiesel by enzyme of compound lipases is improved effect.
The result of table 11000g changing food waste production biofuel
Claims (10)
1. utilize pre-treatment to improve a method for meal kitchen grease process for preparing biodiesel by enzyme output, it is characterized in that, comprise the steps:
S1. remove the foreign material in changing food waste, changing food waste is carried out microwave, ultrasonic wave and hydrothermal treatment consists successively;
S2. by the changing food waste three phase separation through S1 process, upper strata grease is obtained;
S3. pass into ozone in the grease obtained to S2 to be oxidized;
S4. add immobilization compound lipases in the grease obtained to S3, and add short chain alcohol and carry out transesterification reaction and prepare biofuel;
Wherein, immobilization compound lipases described in S4 comprises geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase.
2. method according to claim 1, is characterized in that, immobilization compound lipases described in S4 is made up of geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase 1 ~ 10:1 in mass ratio ~ 10:5 ~ 25.
3. method according to claim 1, is characterized in that, passes into ozone make the concentration of ozone in grease be 15 ~ 20g/L to S3.
4. method according to claim 1, it is characterized in that, add in the grease that S3 obtains after compound lipases is hydrolyzed and carry out S4 step again, described compound lipases comprises geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase.
5. method according to claim 4, is characterized in that, compound lipases described in S3 is made up of geotrichum candidum lipase, lipase from candida sp and Burkholderia cepacia lipase 0.2 ~ 6:1 in mass ratio ~ 10:1.5 ~ 15.
6. method according to claim 5, is characterized in that, the compound lipases for being hydrolyzed described in S3 accounts for 0.5 ~ 10% of grease weight, and hydrolysis time is 0.5 ~ 10h, and hydrolysis temperature is 25 ~ 45 DEG C.
7. method according to claim 1, is characterized in that, the power of microwave described in S1 is 100w ~ 2500kw, and the time is 2 ~ 120min, and temperature is 90 ~ 250 DEG C.
8. method according to claim 1, is characterized in that, hyperacoustic power described in S1 is 15 ~ 1500w/L, and the treatment time is 5 ~ 60min.
9. method according to claim 1, is characterized in that, immobilization compound lipases described in S4 accounts for 0.5 ~ 35% of meal kitchen grease weight.
10. method according to claim 1, is characterized in that, the carrier in immobilization compound lipases described in S4 is made up of agriculture and forestry organic waste material that pulverizing.
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Cited By (4)
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