CN105132005A - Preparation method for biodiesel - Google Patents
Preparation method for biodiesel Download PDFInfo
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- CN105132005A CN105132005A CN201510446701.2A CN201510446701A CN105132005A CN 105132005 A CN105132005 A CN 105132005A CN 201510446701 A CN201510446701 A CN 201510446701A CN 105132005 A CN105132005 A CN 105132005A
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 204
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 192
- 235000011187 glycerol Nutrition 0.000 claims abstract description 96
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000011084 recovery Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000000909 electrodialysis Methods 0.000 claims description 64
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000002551 biofuel Substances 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002815 homogeneous catalyst Substances 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 20
- 238000005809 transesterification reaction Methods 0.000 claims description 20
- 230000000694 effects Effects 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 18
- 125000005456 glyceride group Chemical group 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- 235000019198 oils Nutrition 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000002283 diesel fuel Substances 0.000 claims description 9
- 239000003549 soybean oil Substances 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003011 anion exchange membrane Substances 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 3
- 235000020238 sunflower seed Nutrition 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 210000000582 semen Anatomy 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- -1 enter separator I 6 Chemical compound 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004895 Lipoproteins Human genes 0.000 description 1
- 108090001030 Lipoproteins Proteins 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention discloses a preparation method for biodiesel, which belongs to the technical field of oleochemical industry. According to the method, the biodiesel is prepared through ester exchange reaction, product separation, recovery of a catalyst in a crude biodiesel solution and in a crude glycerin solution, recovery of alcohol in the crude biodiesel solution and in the crude glycerin solution, fine filtration and collection of biodiesel and rectification and collection of glycerin, wherein the recovery rate of the catalyst is more than 97%, and biodiesel with purity of more than 98.4% and glycerin with purity of more than 98% are obtained. The method provided by the invention has the advantages of simple process, convenience in operation, high efficiency, no pollution, low energy consumption, cleanness and semi-continuous production.
Description
Technical field
The present invention relates to a kind of method preparing biofuel, particularly a kind of homogeneous catalyst is prepared biofuel and is removed in conjunction with electroosmose process and reclaim the method for catalyzer, belongs to technical field of oil chemical industry.
Background technology
Biofuel refers to Vegetable oil lipoprotein such as oil crops, Wild oil plant and algae, and the methyl esters that to be stock oil made by ester exchange process such as animal grease, biodiesel or ethyl ester fuel.It is a kind of good petrifaction diesel substitute, compared with petrifaction diesel, has the excellent feature of environmental protection, good cryogenic engine startability and safety performance, good fuel performance and the feature such as renewable.
Current industrial production biofuel mainly uses ester-interchange method, and the catalyzer for transesterify has chemical catalyst and biological enzyme agent etc.Chemical catalyst can be homogeneous catalyst and heterogeneous catalyst.Heterogeneous catalyst is presented in out of phase reaction, (such as: solid catalyst is in liquid hybrid reaction), and homogeneous catalyst is then the reaction (such as: liquid catalyst is in liquid hybrid reaction) being presented on same phase.An easy heterogeneous catalytic reaction contains the surface that reactant is adsorbed on catalyzer, the key in reactant causes new key to produce because of fragility very, but insecure because of the key between product and catalyzer, and product is occurred.Homogeneous catalyst comprises liquid acidand basecatalysts, soluble transition metal compound (salt and complex compound) etc.Homogeneous catalyst independently works with molecule or ion, and active centre is homogeneous, has high reactivity and highly selective.Therefore homogeneous catalyst is generally high than heterogeneous catalyst service efficiency, and homogeneous catalyst effectively can accelerate speed of reaction, but the shortcoming of homogeneous catalyst is the postorder process complexity of catalyzer, and must carry out isolation andpurification to product could remove it.The method that general homogeneous catalyst is removed comprises washing and resins exchange, and WATER-WASHING METHOD is relatively more effective, but can bring the problem that wastewater treatment is difficult and biodiesel oil product resistance of oxidation is low; And resins exchange method of purification is effective equally, but resin is more expensive, and the cost of resin regeneration is higher, can produce solid waste after process.But no matter be WATER-WASHING METHOD or exchange resin method, catalyzer eliminates, but catalyzer all can not reclaim again, causes the wasting of resources, running cost increases.Therefore study a kind of problem that can solve the process of homogeneous catalyst postorder and bring, can catalyzer be reclaimed again and the method reduced costs is very promising.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, a kind of method preparing biofuel is newly provided, utilize homogeneous catalyst to prepare biofuel remove in conjunction with electroosmose process and reclaim catalyzer, to overcome the defect that existing preparation method exists, the purity of biofuel improves greatly, and the energy consumption of whole technique and cost reduce greatly.
The method preparing biofuel of the present invention, specifically comprises the following steps:
(1) transesterification reaction: the alcohol in the glyceride stock in head tank 1, alcohol tank 2 and the catalyzer in catalyst tank 3 are entered in main treatment tank 4 continuously with certain proportion and is uniformly mixed, there is transesterification reaction, temperature of reaction is 140 ~ 200 DEG C, and the reaction times is 2 ~ 3 hours;
(2) product separation: the product after main treatment tank enters knockout tower 5, becomes coarse biodiesel solution and Crude glycerin solution by product separation;
(3) recovery of catalyzer in coarse biodiesel solution: isolated coarse biodiesel solution enters electrodialysis unit I 7 from knockout tower 5, from alcohol tank 2, send into alcohol through alcohol transportation pipe 9 simultaneously, after electrodialysis effect, catalyzer in coarse biodiesel solution is taken out of by alcohol, enter separator I 6, catalyzer in alcohol is recovered in catalyst tank 3, and alcohol then enters alcohol transportation pipe 9 to be continued to recycle, and removes the coarse biodiesel solution after catalyzer and then enters alcohol recovery stage;
(4) recovery of catalyzer in Crude glycerin solution: isolated Crude glycerin solution enters electrodialysis unit II 13 from knockout tower 5, from alcohol tank 2, send into alcohol through alcohol transportation pipe 9 simultaneously, after electrodialysis effect, catalyzer in Crude glycerin solution is taken out of by alcohol, enter separator II 12, catalyzer in alcohol is recovered in catalyst tank 3, and alcohol then enters alcohol transportation pipe 9 to be continued to recycle, and removes the Crude glycerin solution after catalyzer and then enters alcohol recovery stage;
(5) recovery of alcohol in coarse biodiesel: coarse biodiesel solution out enters in distiller I 8 and distills from electrodialysis unit I 7, and the recycle of alcohol tank sent back to by the alcohol distilled, and remaining solution enters the biofuel essence filter stage;
(6) recovery of alcohol in raw glycerine: Crude glycerin solution out enters in distiller II 14 and distills from electrodialysis unit II 13, and the recycle of alcohol tank sent back to by the alcohol distilled, and remaining solution enters glycerine stage of rectification;
(7) biofuel essence filter and collecting: coarse biodiesel out enters in secondary filter 10 from distiller 8, is removed by residual impurity, finally obtain refined biometric diesel oil in secondary filter 10, collects and enters in biofuel storage tank 11;
(8) glycerine rectifying and collection: raw glycerine out enters in rectifying tower 15 from distiller II 14, removes impurity, finally obtain finished product glycerine in rectifying tower 15, collects and enters in glycerine storage tank 16.
Glyceride stock described in step of the present invention (1) comprises Semen Maydis oil, soybean oil, rapeseed oil, sunflower seed oil, palm wet goods vegetables oil.
Alcohol described in step of the present invention (1) is monohydroxy-alcohol, comprises methyl alcohol, ethanol, propyl alcohol and butanols, and is anhydrous monohydroxy-alcohol.
Catalyzer described in step of the present invention (1) is homogeneous catalyst of strong base or strong acid homogeneous catalyst, and wherein homogeneous catalyst of strong base comprises potassium hydroxide and sodium hydroxide, and strong acid homogeneous catalyst comprises sulfuric acid, phosphoric acid and hydrochloric acid.
It is 12% ~ 15% that certain proportion described in step of the present invention (1) refers to that alcohol accounts for glyceride stock mass ratio, and it is 0.7% ~ 1% that catalyzer accounts for glyceride stock mass ratio.
In described (2) step, main treatment tank 4 self-carrying mixing and heating unit;
In described (3) step, electrodialysis unit I 7 by direct supply 17, go the reacting product outlet pipe 18 of catalyzer, alcohol outlet pipe 23, reaction product inlet tube 22, alcohol inlet tube 27, positive pole 19, negative pole 24, cationic exchange membrane 20, anion-exchange membrane 25, alcohol circulation road 26 and reaction product passage 21 to form; Be alternately arranged in this device many cationic exchange membranes 20 and anion-exchange membrane 25, is separated into many alcohol circulation roads 26 of being alternately arranged and reaction product passage 21; Galvanic current 17 connects positive pole 19 and negative pole 24, reaction product inlet tube 22 connects reaction product passage 21 inlet end of each correspondence respectively, alcohol inlet tube 27 connects alcohol circulation road 26 inlet end of each correspondence respectively, go the reacting product outlet pipe 18 of catalyzer to connect reaction product passage 21 exit end of each correspondence respectively, alcohol outlet pipe 23 connects alcohol circulation road 26 exit end of each correspondence respectively.Wherein said reaction product is the reaction product after having reacted in main treatment tank 4, i.e. coarse biodiesel solution or Crude glycerin solution.
In described (4) step, electrodialysis unit II 13 is identical with electrodialysis unit I 7 structure.
Advantage of the present invention and positively effect:
(1) electroosmose process is adopted to remove homogeneous catalyst, do not need to consume pharmaceutical chemicals, equipment is simple, easy to operate, namely solve increase that at present conventional WATER-WASHING METHOD the brings step of Separation of Water, the formation of emulsification and the product instability problem that causes because of the existence of water in products from product, solve again the problem that the resin regeneration cost that adopts ion exchange method to bring is high;
(2) carry out catalyzer electrodialysis and recycling respectively to the coarse biodiesel solution after transesterification reaction and Crude glycerin solution respectively, the rate of recovery reaches more than 97%, saves the cost of whole system;
(3) in whole technique, monohydroxy-alcohol both participated in transesterification reaction, and again as the carrier in electrodialysis process, its recovery utilization rate is greatly enhanced.
(4) this technique can obtain the biofuel that purity is more than 98.4%, and purity is more than 98% glycerine, and this inventive method has that technique is simple, easy to operate, efficiency is high, pollution-free, energy consumption is low, the advantage of process cleans and semi-successive cultivation.
Accompanying drawing explanation
Fig. 1 is technical process of the present invention;
In figure: 1-head tank; 2-alcohol tank; 3-catalyst tank; 4-main treatment tank; 5-knockout tower; 6-separator I; 7-electrodialysis unit I; 8-distiller; 9-alcohol transportation pipe; 10-secondary filter; 11-biofuel storage tank; 12-separator II; 13-electrodialysis unit II; 14-distiller II; 15-rectifying tower; 16-glycerine storage tank;
Fig. 2 is electrodialysis unit schematic diagram of the present invention;
In figure: 17-direct supply; 18-removes the reacting product outlet pipe of catalyzer; 19-positive pole; 20-cationic exchange membrane; 21-reaction product passage; 22-reaction product inlet tube; 23-alcohol outlet pipe; 24-negative pole; 25-anion-exchange membrane; 26-alcohol circulation road; 27-alcohol inlet tube.
Embodiment
Embodiment 1: as shown in Figure 1-2, a kind of method preparing biofuel:
First 10kg soybean oil, 1.3kg methyl alcohol and 70gNaOH catalyzer are entered continuously in main treatment tank 4 and be uniformly mixed, transesterification reaction occurs, and temperature of reaction is 160 DEG C, and the reaction times is 2.5 hours.Product after main treatment tank enters knockout tower 5, product separation is become coarse biodiesel solution and Crude glycerin solution, from knockout tower 5, isolated coarse biodiesel solution enters electrodialysis unit I 7, after electrodialysis effect, NaOH in coarse biodiesel solution is taken out of by methyl alcohol, enter separator I 6, NaOH in methyl alcohol is recovered in catalyst tank 3, reclaim NaOH catalyzer 42.4g, methyl alcohol then enters alcohol transportation pipe 9 to be continued to recycle, from electrodialysis unit I 7, coarse biodiesel solution out enters in distiller I 8 and distills, the methyl alcohol distilled sends the recycle of alcohol tank back to, from distiller 8, coarse biodiesel out enters in secondary filter 10, in secondary filter 10, residual impurity is removed, finally obtain the refined biometric diesel oil that purity is 98.6%, collection enters in biofuel storage tank 11,
Simultaneously, from knockout tower 5, isolated Crude glycerin solution enters electrodialysis unit II 13, after electrodialysis effect, NaOH in Crude glycerin solution is taken out of by methyl alcohol, enter separator II 12, NaOH in methyl alcohol is recovered in catalyst tank 3, reclaim NaOH catalyzer 25.7g, methyl alcohol then enters alcohol transportation pipe 9 to be continued to recycle, from electrodialysis unit II 13, Crude glycerin solution out enters in distiller II 14 and distills, the recycle of alcohol tank sent back to by the alcohol distilled, from distiller II 14, raw glycerine out enters in rectifying tower 15, impurity is removed in rectifying tower 15, finally obtaining purity is 98.3% finished product glycerine, collection enters in glycerine storage tank 16.
Embodiment 2: as shown in Figure 1-2, a kind of method preparing biofuel:
First 10kg rapeseed oil, 1.4kg ethanol and 80gNaOH catalyzer are entered continuously in main treatment tank 4 and be uniformly mixed, transesterification reaction occurs, and temperature of reaction is 170 DEG C, and the reaction times is 2.5 hours.Product after main treatment tank enters knockout tower 5, product separation is become coarse biodiesel solution and Crude glycerin solution, from knockout tower 5, isolated coarse biodiesel solution enters electrodialysis unit I 7, after electrodialysis effect, NaOH in coarse biodiesel solution is taken out of by ethanol, enter separator I 6, NaOH in ethanol is recovered in catalyst tank 3, reclaim NaOH catalyzer 44.2g, ethanol then enters alcohol transportation pipe 9 to be continued to recycle, from electrodialysis unit I 7, coarse biodiesel solution out enters in distiller I 8 and distills, the recycle of alcohol tank sent back to by the ethanol distilled, from distiller 8, coarse biodiesel out enters in secondary filter 10, in secondary filter 10, residual impurity is removed, finally obtain the refined biometric diesel oil that purity is 98.5%, collection enters in biofuel storage tank 11,
Simultaneously, from knockout tower 5, isolated Crude glycerin solution enters electrodialysis unit II 13, after electrodialysis effect, NaOH in Crude glycerin solution is taken out of by ethanol, enter separator II 12, NaOH in ethanol is recovered in catalyst tank 3, reclaim NaOH catalyzer 33.9g, ethanol then enters alcohol transportation pipe 9 to be continued to recycle, from electrodialysis unit II 13, Crude glycerin solution out enters in distiller II 14 and distills, the recycle of alcohol tank sent back to by the ethanol distilled, from distiller II 14, raw glycerine out enters in rectifying tower 15, impurity is removed in rectifying tower 15, finally obtaining purity is 98.6% finished product glycerine, collection enters in glycerine storage tank 16.
Embodiment 3: as shown in Figure 1-2, a kind of method preparing biofuel:
First 10kg sunflower seed oil, 1.4kg ethanol and 90g sulfuric acid catalyst are entered continuously in main treatment tank 4 and be uniformly mixed, transesterification reaction occurs, and temperature of reaction is 180 DEG C, and the reaction times is 3 hours.Product after main treatment tank enters knockout tower 5, product separation is become coarse biodiesel solution and Crude glycerin solution, from knockout tower 5, isolated coarse biodiesel solution enters electrodialysis unit I 7, after electrodialysis effect, sulfuric acid in coarse biodiesel solution is taken out of by ethanol, enter separator I 6, sulfuric acid in ethanol is recovered in catalyst tank 3, reclaim(ed) sulfuric acid catalyzer 50.8g, ethanol then enters alcohol transportation pipe 9 to be continued to recycle, from electrodialysis unit I 7, coarse biodiesel solution out enters in distiller I 8 and distills, the recycle of alcohol tank sent back to by the ethanol distilled, from distiller 8, coarse biodiesel out enters in secondary filter 10, in secondary filter 10, residual impurity is removed, finally obtain the refined biometric diesel oil that purity is 98.8%, collection enters in biofuel storage tank 11,
Simultaneously, from knockout tower 5, isolated Crude glycerin solution enters electrodialysis unit II 13, after electrodialysis effect, sulfuric acid in Crude glycerin solution is taken out of by ethanol, enter separator II 12, sulfuric acid in ethanol is recovered in catalyst tank 3, reclaim(ed) sulfuric acid catalyzer 38g, ethanol then enters alcohol transportation pipe 9 to be continued to recycle, from electrodialysis unit II 13, Crude glycerin solution out enters in distiller II 14 and distills, the recycle of alcohol tank sent back to by the ethanol distilled, from distiller II 14, raw glycerine out enters in rectifying tower 15, impurity is removed in rectifying tower 15, finally obtaining purity is 99% finished product glycerine, collection enters in glycerine storage tank 16.
Embodiment 4: as shown in Figure 1-2, a kind of method preparing biofuel:
First 10kg plam oil, 1.4kg propyl alcohol and 85gKOH catalyzer are entered continuously in main treatment tank 4 and be uniformly mixed, transesterification reaction occurs, and temperature of reaction is 200 DEG C, and the reaction times is 2.5 hours.Product after main treatment tank enters knockout tower 5, product separation is become coarse biodiesel solution and Crude glycerin solution, from knockout tower 5, isolated coarse biodiesel solution enters electrodialysis unit I 7, after electrodialysis effect, KOH in coarse biodiesel solution is taken out of by propyl alcohol, enter separator I 6, KOH in propyl alcohol is recovered in catalyst tank 3, reclaim KOH catalyzer 51g, propyl alcohol then enters alcohol transportation pipe 9 to be continued to recycle, from electrodialysis unit I 7, coarse biodiesel solution out enters in distiller I 8 and distills, the recycle of alcohol tank sent back to by the propyl alcohol distilled, from distiller 8, coarse biodiesel out enters in secondary filter 10, in secondary filter 10, residual impurity is removed, finally obtain the refined biometric diesel oil that purity is 98.7%, collection enters in biofuel storage tank 11,
Simultaneously, from knockout tower 5, isolated Crude glycerin solution enters electrodialysis unit II 13, after electrodialysis effect, KOH in Crude glycerin solution is taken out of by propyl alcohol, enter separator II 12, KOH in propyl alcohol is recovered in catalyst tank 3, reclaim KOH catalyzer 32.7g, propyl alcohol then enters alcohol transportation pipe 9 to be continued to recycle, from electrodialysis unit II 13, Crude glycerin solution out enters in distiller II 14 and distills, the recycle of alcohol tank sent back to by the propyl alcohol distilled, from distiller II 14, raw glycerine out enters in rectifying tower 15, impurity is removed in rectifying tower 15, finally obtaining purity is 98.2% finished product glycerine, collection enters in glycerine storage tank 16.
Embodiment 5: as shown in Figure 1-2, a kind of method preparing biofuel: specifically comprise the following steps:
(1) transesterification reaction: the glyceride stock in head tank 1 is adopted soybean oil (10kg), alcohol in alcohol tank 2 adopts the employing of the catalyzer in methyl alcohol (1.2kg) and catalyst tank 3 NaOH(70g) enter continuously in main treatment tank 4 and be uniformly mixed, there is transesterification reaction, temperature of reaction is 140 DEG C, and the reaction times is 2 hours;
(2) product separation: the product after main treatment tank enters knockout tower 5, becomes coarse biodiesel solution and Crude glycerin solution by product separation;
(3) recovery of catalyzer in coarse biodiesel solution: isolated coarse biodiesel solution enters electrodialysis unit I 7 from knockout tower 5, from alcohol tank 2, send into alcohol through alcohol transportation pipe 9 simultaneously, after electrodialysis effect, catalyzer in coarse biodiesel solution is taken out of by alcohol, enter separator I 6, catalyzer in alcohol is recovered in catalyst tank 3, and alcohol then enters alcohol transportation pipe 9 to be continued to recycle, and removes the coarse biodiesel solution after catalyzer and then enters alcohol recovery stage;
(4) recovery of catalyzer in Crude glycerin solution: isolated Crude glycerin solution enters electrodialysis unit II 13 from knockout tower 5, from alcohol tank 2, send into alcohol through alcohol transportation pipe 9 simultaneously, after electrodialysis effect, catalyzer in Crude glycerin solution is taken out of by alcohol, enter separator II 12, catalyzer in alcohol is recovered in catalyst tank 3, and alcohol then enters alcohol transportation pipe 9 to be continued to recycle, and removes the Crude glycerin solution after catalyzer and then enters alcohol recovery stage;
(5) recovery of alcohol in coarse biodiesel: coarse biodiesel solution out enters in distiller I 8 and distills from electrodialysis unit I 7, and the recycle of alcohol tank sent back to by the alcohol distilled, and remaining solution enters the biofuel essence filter stage;
(6) recovery of alcohol in raw glycerine: Crude glycerin solution out enters in distiller II 14 and distills from electrodialysis unit II 13, and the recycle of alcohol tank sent back to by the alcohol distilled, and remaining solution enters glycerine stage of rectification;
(7) biofuel essence filter and collecting: coarse biodiesel out enters in secondary filter 10 from distiller 8, is removed by residual impurity, finally obtain refined biometric diesel oil in secondary filter 10, collects and enters in biofuel storage tank 11;
(8) glycerine rectifying and collection: raw glycerine out enters in rectifying tower 15 from distiller II 14, removes impurity, finally obtain finished product glycerine in rectifying tower 15, collects and enters in glycerine storage tank 16.
Embodiment 6: as shown in Figure 1-2, a kind of method preparing biofuel: specifically comprise the following steps:
(1) transesterification reaction: the alcohol in the glyceride stock in head tank 1, alcohol tank 2 and the catalyzer in catalyst tank 3 are entered in main treatment tank 4 continuously with certain proportion and is uniformly mixed, there is transesterification reaction, temperature of reaction is 140 ~ 200 DEG C, and the reaction times is 2 ~ 3 hours;
(1) transesterification reaction: the glyceride stock in head tank 1 is adopted soybean oil (10kg), alcohol in alcohol tank 2 adopts the employing of the catalyzer in methyl alcohol (1.4kg) and catalyst tank 3 NaOH(80g) enter continuously in main treatment tank 4 and be uniformly mixed, there is transesterification reaction, temperature of reaction is 170 DEG C, and the reaction times is 2.5 hours;
(2) product separation: the product after main treatment tank enters knockout tower 5, becomes coarse biodiesel solution and Crude glycerin solution by product separation;
(3) recovery of catalyzer in coarse biodiesel solution: isolated coarse biodiesel solution enters electrodialysis unit I 7 from knockout tower 5, from alcohol tank 2, send into alcohol through alcohol transportation pipe 9 simultaneously, after electrodialysis effect, catalyzer in coarse biodiesel solution is taken out of by alcohol, enter separator I 6, catalyzer in alcohol is recovered in catalyst tank 3, and alcohol then enters alcohol transportation pipe 9 to be continued to recycle, and removes the coarse biodiesel solution after catalyzer and then enters alcohol recovery stage;
(4) recovery of catalyzer in Crude glycerin solution: isolated Crude glycerin solution enters electrodialysis unit II 13 from knockout tower 5, from alcohol tank 2, send into alcohol through alcohol transportation pipe 9 simultaneously, after electrodialysis effect, catalyzer in Crude glycerin solution is taken out of by alcohol, enter separator II 12, catalyzer in alcohol is recovered in catalyst tank 3, and alcohol then enters alcohol transportation pipe 9 to be continued to recycle, and removes the Crude glycerin solution after catalyzer and then enters alcohol recovery stage;
(5) recovery of alcohol in coarse biodiesel: coarse biodiesel solution out enters in distiller I 8 and distills from electrodialysis unit I 7, and the recycle of alcohol tank sent back to by the alcohol distilled, and remaining solution enters the biofuel essence filter stage;
(6) recovery of alcohol in raw glycerine: Crude glycerin solution out enters in distiller II 14 and distills from electrodialysis unit II 13, and the recycle of alcohol tank sent back to by the alcohol distilled, and remaining solution enters glycerine stage of rectification;
(7) biofuel essence filter and collecting: coarse biodiesel out enters in secondary filter 10 from distiller 8, is removed by residual impurity, finally obtain refined biometric diesel oil in secondary filter 10, collects and enters in biofuel storage tank 11;
(8) glycerine rectifying and collection: raw glycerine out enters in rectifying tower 15 from distiller II 14, removes impurity, finally obtain finished product glycerine in rectifying tower 15, collects and enters in glycerine storage tank 16.
Embodiment 7: as shown in Figure 1-2, a kind of method preparing biofuel: specifically comprise the following steps:
(1) transesterification reaction: the alcohol in the glyceride stock in head tank 1, alcohol tank 2 and the catalyzer in catalyst tank 3 are entered in main treatment tank 4 continuously with certain proportion and is uniformly mixed, there is transesterification reaction, temperature of reaction is 140 ~ 200 DEG C, and the reaction times is 2 ~ 3 hours;
(1) transesterification reaction: the glyceride stock in head tank 1 is adopted soybean oil (10kg), alcohol in alcohol tank 2 adopts the employing of the catalyzer in methyl alcohol (1.5kg) and catalyst tank 3 NaOH(100g) enter continuously in main treatment tank 4 and be uniformly mixed, there is transesterification reaction, temperature of reaction is 200 DEG C, and the reaction times is 3 hours;
(2) product separation: the product after main treatment tank enters knockout tower 5, becomes coarse biodiesel solution and Crude glycerin solution by product separation;
(3) recovery of catalyzer in coarse biodiesel solution: isolated coarse biodiesel solution enters electrodialysis unit I 7 from knockout tower 5, from alcohol tank 2, send into alcohol through alcohol transportation pipe 9 simultaneously, after electrodialysis effect, catalyzer in coarse biodiesel solution is taken out of by alcohol, enter separator I 6, catalyzer in alcohol is recovered in catalyst tank 3, and alcohol then enters alcohol transportation pipe 9 to be continued to recycle, and removes the coarse biodiesel solution after catalyzer and then enters alcohol recovery stage;
(4) recovery of catalyzer in Crude glycerin solution: isolated Crude glycerin solution enters electrodialysis unit II 13 from knockout tower 5, from alcohol tank 2, send into alcohol through alcohol transportation pipe 9 simultaneously, after electrodialysis effect, catalyzer in Crude glycerin solution is taken out of by alcohol, enter separator II 12, catalyzer in alcohol is recovered in catalyst tank 3, and alcohol then enters alcohol transportation pipe 9 to be continued to recycle, and removes the Crude glycerin solution after catalyzer and then enters alcohol recovery stage;
(5) recovery of alcohol in coarse biodiesel: coarse biodiesel solution out enters in distiller I 8 and distills from electrodialysis unit I 7, and the recycle of alcohol tank sent back to by the alcohol distilled, and remaining solution enters the biofuel essence filter stage;
(6) recovery of alcohol in raw glycerine: Crude glycerin solution out enters in distiller II 14 and distills from electrodialysis unit II 13, and the recycle of alcohol tank sent back to by the alcohol distilled, and remaining solution enters glycerine stage of rectification;
(7) biofuel essence filter and collecting: coarse biodiesel out enters in secondary filter 10 from distiller 8, is removed by residual impurity, finally obtain refined biometric diesel oil in secondary filter 10, collects and enters in biofuel storage tank 11;
(8) glycerine rectifying and collection: raw glycerine out enters in rectifying tower 15 from distiller II 14, removes impurity, finally obtain finished product glycerine in rectifying tower 15, collects and enters in glycerine storage tank 16.
By reference to the accompanying drawings the specific embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (6)
1. prepare a method for biofuel, it is characterized in that: the concrete steps of described method are as follows:
(1) transesterification reaction: the alcohol in the glyceride stock in head tank 1, alcohol tank 2 and the catalyzer in catalyst tank 3 are entered in main treatment tank 4 continuously with certain proportion and is uniformly mixed, there is transesterification reaction, temperature of reaction is 140 ~ 200 DEG C, and the reaction times is 2 ~ 3 hours;
(2) product separation: the product after main treatment tank 4 enters knockout tower 5, becomes coarse biodiesel solution and Crude glycerin solution by product separation;
(3) recovery of catalyzer in coarse biodiesel solution: isolated coarse biodiesel solution enters electrodialysis unit I 7 from knockout tower 5, from alcohol tank 2, send into alcohol through alcohol transportation pipe 9 simultaneously, after electrodialysis effect, catalyzer in coarse biodiesel solution is taken out of by alcohol, enter separator I 6, catalyzer in alcohol is recovered in catalyst tank 3, and alcohol then enters alcohol transportation pipe 9 to be continued to recycle, and removes the coarse biodiesel solution after catalyzer and then enters alcohol recovery stage;
(4) recovery of catalyzer in Crude glycerin solution: isolated Crude glycerin solution enters electrodialysis unit II 13 from knockout tower 5, from alcohol tank 2, send into alcohol through alcohol transportation pipe 9 simultaneously, after electrodialysis effect, catalyzer in Crude glycerin solution is taken out of by alcohol, enter separator II 12, catalyzer in alcohol is recovered in catalyst tank 3, and alcohol then enters alcohol transportation pipe 9 to be continued to recycle, and removes the Crude glycerin solution after catalyzer and then enters alcohol recovery stage;
(5) recovery of alcohol in coarse biodiesel: coarse biodiesel solution out enters in distiller I 8 and distills from electrodialysis unit I 7, and the recycle of alcohol tank sent back to by the alcohol distilled, and remaining solution enters the biofuel essence filter stage;
(6) recovery of alcohol in raw glycerine: Crude glycerin solution out enters in distiller II 14 and distills from electrodialysis unit II 13, and the recycle of alcohol tank sent back to by the alcohol distilled, and remaining solution enters glycerine stage of rectification;
(7) biofuel essence filter and collecting: coarse biodiesel out enters in secondary filter 10 from distiller 8, is removed by residual impurity, finally obtain refined biometric diesel oil in secondary filter 10, collects and enters in biofuel storage tank 11;
(8) glycerine rectifying and collection: raw glycerine out enters in rectifying tower 15 from distiller II 14, removes impurity, finally obtain finished product glycerine in rectifying tower 15, collects and enters in glycerine storage tank 16.
2. the method preparing biofuel according to claim 1, is characterized in that: described glyceride stock is that Semen Maydis oil, soybean oil, rapeseed oil, sunflower seed oil, plam oil are wherein a kind of.
3. the method preparing biofuel according to claim 1, is characterized in that: described alcohol is monohydroxy-alcohol, comprises methyl alcohol, ethanol, propyl alcohol and butanols wherein a kind of, and be anhydrous monohydroxy-alcohol.
4. the method preparing biofuel according to claim 1, it is characterized in that: described catalyzer is homogeneous catalyst of strong base or strong acid homogeneous catalyst, wherein homogeneous catalyst of strong base comprises potassium hydroxide and sodium hydroxide, and strong acid homogeneous catalyst comprises sulfuric acid, phosphoric acid and hydrochloric acid.
5. the method preparing biofuel according to claim 1, is characterized in that: it is 12% ~ 15% that described certain proportion refers to that alcohol accounts for glyceride stock mass ratio, and it is 0.7% ~ 1% that catalyzer accounts for glyceride stock mass ratio.
6. the method preparing biofuel according to claim 1, is characterized in that: described electrodialysis unit I (7) by direct supply (17), go the reacting product outlet pipe (18) of catalyzer, alcohol outlet pipe (23), reaction product inlet tube (22), alcohol inlet tube (27), positive pole (19), negative pole (24), cationic exchange membrane (20), anion-exchange membrane (25), alcohol circulation road (26) and reaction product passage (21) to form, be alternately arranged in described electrodialysis unit I (7) cationic exchange membrane (20) and anion-exchange membrane (25), thus be separated into the alcohol circulation road (26) and reaction product passage (21) that are alternately arranged, galvanic current (17) connects positive pole (19) and negative pole (24), reaction product inlet tube (22) connects reaction product passage (21) inlet end of each correspondence respectively, alcohol inlet tube (27) connects alcohol circulation road (26) inlet end of each correspondence respectively, the reacting product outlet pipe (18) of catalyzer is gone to connect reaction product passage (21) exit end of each correspondence respectively, alcohol outlet pipe (23) connects alcohol circulation road (26) exit end of each correspondence respectively, wherein said reaction product is the reaction product after having reacted in main treatment tank 4, i.e. coarse biodiesel solution or Crude glycerin solution.
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| CN108219981A (en) * | 2016-12-22 | 2018-06-29 | 内蒙古中细软技术开发有限公司 | Base catalysis method biodiesel synthesis |
| CN114950503A (en) * | 2021-12-21 | 2022-08-30 | 常州市金坛区维格生物科技有限公司 | Preparation method and application of regenerated acid catalyst |
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Application publication date: 20151209 |