CN104403805B - Biodiesel preparation method - Google Patents
Biodiesel preparation method Download PDFInfo
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- CN104403805B CN104403805B CN201410512292.7A CN201410512292A CN104403805B CN 104403805 B CN104403805 B CN 104403805B CN 201410512292 A CN201410512292 A CN 201410512292A CN 104403805 B CN104403805 B CN 104403805B
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- Prior art keywords
- alcohol
- ester
- short chain
- biodiesel
- oil
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 alcohol ester Chemical class 0.000 claims abstract description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 39
- 229930195729 fatty acid Natural products 0.000 claims abstract description 39
- 239000000194 fatty acid Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 235000011187 glycerol Nutrition 0.000 claims abstract description 30
- 239000004519 grease Substances 0.000 claims abstract description 26
- 150000002148 esters Chemical class 0.000 claims abstract description 23
- 239000011973 solid acid Substances 0.000 claims abstract description 22
- 238000010008 shearing Methods 0.000 claims abstract description 13
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 3
- 239000012530 fluid Substances 0.000 claims description 38
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000006227 byproduct Substances 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 16
- 235000019198 oils Nutrition 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 239000002283 diesel fuel Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 230000001413 cellular effect Effects 0.000 claims description 7
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007171 acid catalysis Methods 0.000 claims description 4
- 239000000787 lecithin Substances 0.000 claims description 4
- 235000010445 lecithin Nutrition 0.000 claims description 4
- 229940067606 lecithin Drugs 0.000 claims description 4
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 229960003237 betaine Drugs 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 235000012343 cottonseed oil Nutrition 0.000 claims description 3
- 239000002385 cottonseed oil Substances 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 229920000263 Rubber seed oil Polymers 0.000 claims description 2
- 239000010775 animal oil Substances 0.000 claims description 2
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010806 kitchen waste Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 99
- 235000019441 ethanol Nutrition 0.000 description 70
- 102000004190 Enzymes Human genes 0.000 description 10
- 108090000790 Enzymes Proteins 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 235000009508 confectionery Nutrition 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 125000005456 glyceride group Chemical group 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000012075 bio-oil Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention provides a biodiesel preparation method, the method is characterized in that through a piston compressor, grease and a short chain alcoholic solution enable high speed movement under shearing and high pressure condition, the alcohol ester mixed solution is capable of rapidly forming a reaction interface in continuous movement, an ester interchange reaction can be rapidly completed by a porous solid acid catalyst plate, pressure can be rapidly released from a channel outlet of the piston compressor, the reaction products are introduced in a rotation separating machine, short chain alcohol is condensed and recovered, fatty acid ester and glycerin are separated through the rotation separator, and then continuous recovery is carried out. The method realizes the continuous preparation of biodiesel, environmental pollution can be avoided, conversion rate of grease to biodiesel can be greatly increased, and new technology for producing biodiesel with a continuous, cleaning and high efficiency mode is established.
Description
Technical field
The present invention relates to bio-fuel field is and in particular to a kind of preparation method of biodiesel.
Background technology
Biodiesel is the biomass fuel that extract from renewable fat or grease, due to general vegetable oil and dynamic
Thing oil molecule is 14～18 carbochain compositions, extremely similar to the diesel fuel characteristicses of the carbochain composition of 15 about, therefore biological bavin
Oil is used directly for Diesel engine or is used in mixed way with diesel oil.Biodiesel can be regenerated due to its raw material, shows
The good feature of environmental protection and sustainability, become the good substitute of diesel oil.And biodiesel compared with petroleum diesel also with
Lower advantage:In biodiesel sulfur content low so that the discharge of sulfur dioxide and sulfide is low, can reduce by about 30% sulphur emissions；Raw
Do not contain, in thing diesel oil, the aromatic series alkane that environment can be polluted, thus waste gas is less than petroleum diesel to human body infringement；Biological
The biological degradability of diesel oil is high；- 20 DEG C of biodiesel condensation point, has preferable cryogenic engine startability, resistance to frost
Excellent；Biodiesel flash-point is low, is not belonging to dangerous material；Cetane number is high, has good fuel performance.
The primary raw material of biodiesel is animal and plant fat, can carry out ester exchange reaction by grease and short chain alcohol and be obtained
Fatty acid ester, contains the byproduct such as glycerine, monoglyceride, two sweet esters in fatty acid ester, can get biodiesel by separating.
Ester exchange reaction preparation biodiesel when, due to adopt technique and condition difference can be divided into chemical method, supercritical methanol technology and
Biological enzyme.Wherein chemical method is mainly acid catalyzed process, base catalysis method, needs to use bronsted lowry acids and bases bronsted lowry it is necessary to being neutralized and washing,
Thus producing substantial amounts of sewage, and can not reuse, bringing higher catalyst cost；Supercritical methanol technology technique needs high temperature
High pressure, reaction rate is fast, high conversion rate, pollution-free, but investment and operating cost are high, and technology stability difference is it is difficult to control；Biological
Enzyme process reaction condition is gentle, non-pollutant discharge and need not washing, but catalyzing enzyme high expensive, and react slow, efficiency is low.
Chinese invention patent publication number CN1473907A discloses a kind of production method of biodiesel, and the method includes making
Material vacuum is dehydrated, more in the presence of a catalyst esterification occurs, using inorganic acid (as sulfuric acid, hydrochloric acid, phosphoric acid) and
Organic acid (as p-methyl benzenesulfonic acid, DBSA, naphthalene sulfonic acids) compounding as catalyst.The method is acid catalysis
Method, shortcoming is that reaction speed is slow, can produce substantial amounts of spent acid product and waste water, thus leading to pollute environment.
Chinese invention patent 1916114 discloses a kind of continuous, homogeneous method preparing biodiesel, and the method will be natural
Grease etc. and methyl alcohol and alkali metal hydroxide and mixed liquor can be made to form homogeneous organic solvent jointly mix, form homogeneous body
System, sends into pipeline reactor and carries out continuous esterification preparation biodiesel.The method enables grease fully to dissolve each other with methyl alcohol,
Accelerate reaction rate, shorten the reaction time, but due to using alkali metal hydroxide as catalyst, therefore, rotten to equipment
Erosion is serious, and base catalyst loss is big, there is pollution.
Chinese invention patent publication number CN1472280A discloses a kind of method of utilization glyceride stock biodiesel synthesis,
The method, using short-chain aliphatic ester as acyl acceptor, carries out transesterification reaction, enzyme catalysis method using biological enzyme bio-oil
Shortcoming be that reaction time length, efficiency are low, enzyme expensive, and enzyme easily inactivates in high purity methanol.
Chinese invention patent 101550349 discloses a kind of method of use preparing biodiesel by supercritical technology, the method
Acidified for various greases eliminating water, esterification, grease after treatment and the suitable mol ratio of methyl alcohol are become equal under overcritical
Phase, carries out ester exchange reaction, and control pressure is 8-40MPA, temperature 300-450 DEG C.This invention shortens bio-oil conversion life
The pollution of the time of thing diesel oil, alkali-free or acid catalyst.But because the method for preparing biodiesel under supercritical condition needs in high temperature height
Carry out under the conditions of pressure, lead to higher producing cost and energy ezpenditure, and belong to batch production, technology stability is poor, especially
It is that high temperature is easily caused biodiesel coking.
Chinese invention patent CN101096602 discloses a kind of method party of continuous synthesis of biodiesel without catalyst
Method first will carry nonpolar grease to carry out electromagnetization process, make grease molecular band polarized, then by the methyl alcohol of polarity and with pole
Property grease simultaneously continuously input high shear Homogenizing pump carry out crosslinking, dissolve each other and homogeneous disposal so that formed grease and
The single-phase miscible solutions of methyl alcohol.The polarity that the method passes through to change reaction phase improves reaction efficiency thus increasing intersolubility, from
And eliminate catalyst.But due to having lacked catalyst, therefore need higher temperature, pressure and longer anti-in the reactor
Between seasonable, step reaction leads to efficiency step-down.
The technique of Chinese invention patent CN101070480A description is grease with alcohol after ester exchange, boils off alcohol, separates
Glycerine, then rectification under vacuum purification, obtains the aliphatic acid low-carbon-ester that concentration reaches 99.0%, but due to aliphatic acid low-carbon-ester
Boiling point higher, about 250-400 DEG C, to rectifying condition require higher.Therefore, the separation of biodiesel directly affects quality.
According to above-mentioned, because biodiesel raw material is complex, in the biodiesel of preparation, contain the various polarity such as glycerine
Byproduct, adds catalyst and excessive methanol etc., further results in the complexity of product, all causes difficulty to separating, reclaiming, especially
It is that there is catalyst contamination during using acid-base catalysis method preparation biodiesel and reclaim；Using catalyzed by biological enzyme to the greatest extent
Pipe does not pollute, but reaction efficiency is low, catalyst high cost；Using supercritical process, due to belonging to batch production, technique is steady
Qualitative difference is it is difficult to control, and is easily caused biodiesel coking degraded under high energy consumption, especially high-temperature and high-pressure conditions.In addition,
Glycerine, as the accessory substance of production of biodiesel, easily gathers in polarity phase (methyl alcohol), and the balance according to reaction,
Easily the fatty acid ester another mistake being obtained is converted into glyceride, thus it is impossible to make grease be fully converted to biodiesel.
Content of the invention
For current preparation biodiesel exist acid base catalysator pollution environment, biological enzyme efficiency low, overcritical
The unmanageable defect of formula of having a rest technique, the present invention provides one kind to prepare biodiesel process.The method passes through piston compressor,
Grease and short chain alcoholic solution is made to obtain motion at high speed under shearing and condition of high voltage, alcohol ester miscible fluid is quickly formed in continuous moving
Reaction interface, is rapidly completed ester exchange reaction by porous solid acid catalyst plate, and further, the method passes through piston compressor
Channel outlet quick release pressure, make product enter rotating separation machine, short chain alcohol reclaims by condensation, fatty acid ester and
Glycerine isopolarity byproduct passes through rotating separation machine and separates, and continuously reclaims.The present invention not only achieves the biological bavin of continuous preparation
Oil, and catalyst attrition is greatly decreased, it is to avoid the pollution to environment, improves the conversion ratio to biodiesel for the grease, opens
Continuous, cleaning, the efficient new technology producing biodiesel are warded off.
The present invention adopts the following technical scheme that realization：
1. a kind of method preparing biodiesel, is characterized in that the shearing by piston compressor and high pressure, make grease with
Short chain alcoholic solution obtains motion at high speed, is rapidly completed ester exchange reaction by porous solid acid catalyst plate, realizes continuous preparation
Biodiesel, concrete preparation method is as follows：
1）By short chain alcohol with activator with mass ratio 2：0.01-0.1 mixes, and forms activation by dispersion machine Forced Dispersion short
Chain alcohol；
2）By grease and step 2) the activation short chain alcohol that obtains is by aliphatic acid and short chain alcohol mol ratio 1:1.0-1.5 is in mixing
It is heated to 40-60 DEG C in machine, after stirring 13-20min, form alcohol ester miscible fluid；
3）By step 2) the alcohol ester miscible fluid that obtains sends into piston compressor, and alcohol ester miscible fluid is in high pressure and shear action
Under, obtain and move and gasify at high speed, make alcohol ester miscible fluid quickly form reaction interface, fast by porous solid acid catalyst plate
Speed completes ester exchange reaction, forms fatty acid ester；
4）The fatty acid ester being obtained by piston compressor and excessive short chain alcohol, glycerin by-product product are in the fast quick-release of channel outlet
Bleed off pressure power, enter rotating separation machine, short chain alcohol is reclaimed by condensation, and fatty acid ester is divided by rotating separation machine with byproduct glycerine
From rear continuous recovery, obtain biodiesel.
Above-mentioned preparation process 1）Described short chain alcohol is C1-C4 alcohol.
Above-mentioned preparation process 1）Described activator is from stearic acid, neopelex, lecithin, glycine betaine
One of type activating agent.
Above-mentioned preparation process 1）Described dispersion machine is to make relative high-speed rotation by rotor with the stator matching, and makes short chain
Alcohol under spiral impulsive force, gap between the stator and the rotor be subject to powerful shearing force, frictional force, make effectively to emulsify,
Dispersion, so that short chain alcohol is hydroxy activated.Above-mentioned preparation process 2）Described grease is vegetable oil, including linseed oil, soybean
Oil, rubber seed oil, castor oil, cottonseed oil, rapeseed oil, also can be selected for kitchen waste oil, animal oil, but need preliminary refining to process.
Above-mentioned preparation process 3）Described piston compressor is continuous high pressure, the reciprocating consersion unit of high shear, utilizes
Oil bath temperature control at 100-140 DEG C, the operation pressure of setting constant in 3-5MPa, piston setting compressor setting alcohol ester miscible fluid adds
Material hole, setting cellular solid acid catalyst plate in piston, when alcohol ester miscible fluid passes through porosu solid acid catalysis plate under high pressure
Liquid reaction interface increases, and is rapidly completed ester exchange reaction.
Above-mentioned preparation process 3）In described piston compressor, setting cellular solid acid catalyst plate, is cellular porous
Solid acid catalyst plate, by cordierite powder after the sulfuric acid solution of 15 ~ 50wt% soaks 24 hours at 50-60 DEG C, and does
The dry porous plate that is supported on is formed.
A kind of method preparing biodiesel of the present invention, by shearing and the high pressure of piston compressor, makes grease and short chain
Alcoholic solution obtains motion at high speed, setting cellular solid acid catalyst plate in piston, and alcohol ester miscible fluid passes through porous under high pressure
During solid acid catalysis plate, liquid reaction interface increases, and is rapidly completed ester exchange reaction, realizes continuous preparation biodiesel.Logical
Cross the channel outlet quick release pressure of piston compressor, short chain alcohol in product can be made to condense and reclaim, fatty acid ester with
Byproduct glycerine is continuously separated by rotating separation machine, forms closed continuous production of biodiesel.Avoid acid base catalysator
Preparation biodiesel is low to the pollution of environment, biological enzyme efficiency, the unmanageable defect of supercritical process batch (-type).Especially
It is the ester exchange reaction by continuous high speed fluid, it is to avoid under high-temperature and high-pressure conditions, be easily caused biodiesel coking degraded
Defect, reclaim short chain alcohol in continuous production in time, it is to avoid polarity methyl alcohol gathers in glycerine, effectively prevents fatty acid ester again
Reverse turns to glyceride, and conversion ratio from grease to biodiesel is greatly improved.
A kind of method preparing biodiesel proposed by the present invention, opens continuous, cleaning, efficient production biodiesel
New technology, technical process non-wastewater discharge；Conversion rate of products reaches more than 97%, and the acid number of biodiesel is less than 0.3mgKOH/g,
Free glycerol content is less than 0.01%, and total amounts of glycerol is less than 0.06%, is fully achieved national biodiesel GB/T20828-2007
Standard.
Brief description
Fig. 1 is the piston compressor continuous ester exchange schematic diagram that a kind of method preparing biodiesel of the present invention is adopted.
A kind of method preparing biodiesel of the present invention, its prominent feature and beneficial effect are：
1st, the method that the present invention prepares biodiesel, by shearing and the high pressure of piston compressor, makes grease and short chain alcohol
Solution obtains motion at high speed, is rapidly completed ester exchange reaction by porous solid acid catalyst plate, realizes the biological bavin of continuous preparation
Oil.
2nd, the method that the present invention prepares biodiesel, avoids HTHP by the ester exchange reaction of continuous high speed fluid
Under the conditions of be easily caused the defect of biodiesel coking degraded, continuous production is reclaimed short chain alcohol in time, it is to avoid polarity first
Alcohol gathers in glycerine, effectively prevents fatty acid ester another mistake to be converted into glyceride, and grease turning to biodiesel is greatly improved
Rate, conversion rate of products reaches more than 97%.
3rd, the method that the present invention prepares biodiesel, opens continuous, cleaning, the efficient new technology producing biodiesel,
Technical process non-wastewater discharge, is suitable for mass producing.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as the present invention
Scope be only limitted to Examples below.In the case of without departing from said method thought of the present invention, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
1）By short chain alcohol methyl alcohol with activator stearic acid with mass ratio 2：0.05 mixing, by dispersion machine Forced Dispersion, first
Alcohol under spiral impulsive force, gap between the stator and the rotor be subject to powerful shearing force, frictional force, make effectively to emulsify,
Dispersion, so that methyl alcohol is hydroxy activated, forms activation methyl alcohol；
2）By cottonseed oil and step 2) the activation methyl alcohol that obtains is by aliphatic acid and alcohol mol ratio 1:1.0 heat in mixer
To 60 DEG C, after stirring 20min, form alcohol ester miscible fluid；
3）By step 2) the alcohol ester miscible fluid that obtains sends into piston compressor, and alcohol ester miscible fluid is in high pressure and shear action
Under, obtain and move at high speed, make alcohol ester miscible fluid quickly form reaction interface, be rapidly completed by porous solid acid catalyst plate
Ester exchange reaction, forms fatty acid ester；
4）The fatty acid ester being obtained by piston compressor and excessive methanol, glycerin by-product product are in channel outlet quick release
Pressure, enters rotating separation machine, and methyl alcohol is reclaimed by condensation, and fatty acid ester passes through rotating separation machine with byproduct glycerine, separates
Speed is 120rpm, and it is to have nonpolar fatty acid ester to separate outside rotary fluid that mixture rotates light component during motion
Place layer, restructuring is divided into polarity glycerine to separate the lower floor within eddy flow, when separator reaches drainage system, heavy constituent sweet
The fatty acid ester of oil and light component is discharged by continuous drainage respectively.
By test, embodiment 1 grease is 97% to biodiesel conversion rate, and the biodiesel performance indications obtaining are complete
Be up to state standards GB/T20828-2007《Diesel fuel mediation biodiesel》Key index, specific targets are as follows：
Embodiment 2
1）By short chain alcohol ethanol with activator neopelex with mass ratio 2：0.02 mixing, strong by dispersion machine
System dispersion, under spiral impulsive force, gap between the stator and the rotor is subject to powerful shearing force, frictional force, has made ethanol
The emulsification of effect ground, dispersion, so that ethanol is hydroxy activated, form activation ethanol；
2）By rapeseed oil and step 2) the activation ethanol that obtains is by aliphatic acid and alcohol mol ratio 1:1.2 mixing, add vegetable seed
The triethanolamine of the 0.05% of oil quality, as catalyst, is heated to 50 DEG C in mixer, forms alcohol ester and mix after stirring 13min
Solution；
3）By step 2) the alcohol ester miscible fluid that obtains sends into piston compressor, and alcohol ester miscible fluid is in high pressure and shear action
Under, obtain and move at high speed, make alcohol ester miscible fluid quickly form reaction interface, be rapidly completed by porous solid acid catalyst plate
Ester exchange reaction, forms fatty acid ester；
4）The fatty acid ester being obtained by piston compressor and excess ethyl alcohol, glycerin by-product product are in channel outlet quick release
Pressure, enters rotating separation machine, and ethanol is reclaimed by condensation, and fatty acid ester passes through rotating separation machine with byproduct glycerine, separates
Speed is 150rpm, and it is to have nonpolar fatty acid ester to separate outside rotary fluid that mixture rotates light component during motion
Place layer, restructuring is divided into polarity glycerine to separate the lower floor within eddy flow, when separator reaches drainage system, heavy constituent sweet
The fatty acid ester of oil and light component is discharged by continuous drainage respectively.
By test, the biodiesel performance indications that embodiment 2 obtains are fully achieved standard GB/T/T20828-2007
《Diesel fuel mediation biodiesel》Key index, specific targets are as follows：
Embodiment 3
1）By short chain alcohol methyl alcohol with activator lecithin with mass ratio 2：0.08 mixing, by dispersion machine Forced Dispersion, first
Alcohol under spiral impulsive force, gap between the stator and the rotor be subject to powerful shearing force, frictional force, make effectively to emulsify,
Dispersion, so that methyl alcohol is hydroxy activated, forms activation methyl alcohol；
2）Kitchen is refined grease and step 2) the activation methyl alcohol that obtains is by aliphatic acid and alcohol mol ratio 1:1.2 in mixer
In be heated to 60 DEG C, stirring 13min after formed alcohol ester miscible fluid；
3）By step 2) the alcohol ester miscible fluid that obtains sends into piston compressor, and alcohol ester miscible fluid is in high pressure and shear action
Under, obtain and move at high speed, make alcohol ester miscible fluid quickly form reaction interface, be rapidly completed by porous solid acid catalyst plate
Ester exchange reaction, forms fatty acid ester；
4）The fatty acid ester being obtained by piston compressor and excessive methanol, glycerin by-product product are in channel outlet quick release
Pressure, enters rotating separation machine, and methyl alcohol is reclaimed by condensation, and fatty acid ester passes through rotating separation machine with byproduct glycerine, separates
Speed is 180rpm, and it is to have nonpolar fatty acid ester to separate outside rotary fluid that mixture rotates light component during motion
Place layer, restructuring is divided into polarity glycerine to separate the lower floor within eddy flow, when separator reaches drainage system, heavy constituent sweet
The fatty acid ester of oil and light component is discharged by continuous drainage respectively.
By test, the biodiesel performance indications that embodiment 3 obtains are fully achieved standard GB/T/T20828-2007
《Diesel fuel mediation biodiesel》Key index, specific targets are as follows：
Embodiment 4
1）By in short chain alcohol methyl alcohol and activator betaine type activating agent with mass ratio 2：0.1 mixing, strong by dispersion machine
System dispersion, under spiral impulsive force, gap between the stator and the rotor is subject to powerful shearing force, frictional force, has made methyl alcohol
The emulsification of effect ground, dispersion, so that methyl alcohol is hydroxy activated, form activation methyl alcohol；
2）By soybean oil and step 2) the activation methyl alcohol that obtains is by aliphatic acid and alcohol mol ratio 1:1.2 mixing, add soybean
The guanidine of oil quality 0.1%, as catalyst, is heated to 40 DEG C in mixer, forms alcohol ester miscible fluid after stirring 15min；
3）By step 2) the alcohol ester miscible fluid that obtains sends into piston compressor, and alcohol ester miscible fluid is in high pressure and shear action
Under, obtain and move at high speed, make alcohol ester miscible fluid quickly form reaction interface, be rapidly completed by porous solid acid catalyst plate
Ester exchange reaction, forms fatty acid ester；
4）The fatty acid ester being obtained by piston compressor and excessive methanol, glycerin by-product product are in channel outlet quick release
Pressure, enters rotating separation machine, and methyl alcohol is reclaimed by condensation, and fatty acid ester passes through rotating separation machine with byproduct glycerine, separates
Speed is 150rpm, and it is to have nonpolar fatty acid ester to separate outside rotary fluid that mixture rotates light component during motion
Place layer, restructuring is divided into polarity glycerine to separate the lower floor within eddy flow, when separator reaches drainage system, heavy constituent sweet
The fatty acid ester of oil and light component is discharged by continuous drainage respectively.
Embodiment 5
1）By short chain alcohol ethanol with activator lecithin with mass ratio 2：0.1 mixing, by dispersion machine Forced Dispersion, ethanol
Under spiral impulsive force, gap between the stator and the rotor is subject to powerful shearing force, frictional force, makes effectively to emulsify, divides
Dissipate, so that methyl alcohol is hydroxy activated, form activation ethanol；
2）By castor oil and step 2) the activation methyl alcohol that obtains is by aliphatic acid and alcohol mol ratio 1:1.5 heat in mixer
To 60 DEG C, after stirring 15min, form alcohol ester miscible fluid；
3）By step 2) the alcohol ester miscible fluid that obtains sends into piston compressor, and alcohol ester miscible fluid is in high pressure and shear action
Under, obtain and move at high speed, make alcohol ester miscible fluid quickly form reaction interface, be rapidly completed by porous solid acid catalyst plate
Ester exchange reaction, forms fatty acid ester；
4）The fatty acid ester being obtained by piston compressor and excess ethyl alcohol, glycerin by-product product are in channel outlet quick release
Pressure, enters rotating separation machine, and methyl alcohol is reclaimed by condensation, and fatty acid ester passes through rotating separation machine with byproduct glycerine, separates
Speed is 150rpm, and it is to have nonpolar fatty acid ester to separate outside rotary fluid that mixture rotates light component during motion
Place layer, restructuring is divided into polarity glycerine to separate the lower floor within eddy flow, when separator reaches drainage system, heavy constituent sweet
The fatty acid ester of oil and light component is discharged by continuous drainage respectively.
Claims (4)
1. a kind of method preparing biodiesel, is characterized in that the shearing by piston compressor and high pressure, makes grease and short chain
Alcoholic solution obtains motion at high speed, is rapidly completed ester exchange reaction by porous solid acid catalyst plate, realizes continuous preparation biological
Diesel oil, concrete preparation method is as follows：
1）By short chain alcohol with activator with mass ratio 2：0.01-0.1 mixes, and forms activation short chain by dispersion machine Forced Dispersion
Alcohol；
2）By grease and step 2) the activation short chain alcohol that obtains is by aliphatic acid and short chain alcohol mol ratio 1:1.0-1.5 is in mixer
In be heated to 40-60 DEG C, stirring 13-20min after formed alcohol ester miscible fluid；
3）By step 2) the alcohol ester miscible fluid that obtains sends into piston compressor, and alcohol ester miscible fluid, under high pressure and shear action, obtains
Obtain and move at high speed, make alcohol ester miscible fluid quickly form reaction interface, ester is rapidly completed by porous solid acid catalyst plate and hands over
Change reaction, form fatty acid ester；
4）The fatty acid ester being obtained by piston compressor and excessive short chain alcohol, glycerin by-product product are in channel outlet quick release pressure
Power, enters rotating separation machine, short chain alcohol is reclaimed by condensation, after fatty acid ester is separated by rotating separation machine with byproduct glycerine
Continuous recovery, obtains biodiesel；
Wherein, preparation process 1）Described dispersion machine is to make relative high-speed rotation by rotor with the stator matching, and makes short chain alcohol
Under spiral impulsive force, gap between the stator and the rotor is subject to powerful shearing force, frictional force, makes effectively to emulsify, divides
Dissipate, so that short chain alcohol is hydroxy activated；
Preparation process 3）Described piston compressor is continuous high pressure, the reciprocating consersion unit of high shear, using oil bath temperature control
At 100-140 DEG C, the constant setting cellular solid acid catalyst plate in 3-5MPa, piston of operation pressure of setting, alcohol ester mixes
Solution passes through liquid reaction interface during porosu solid acid catalysis plate under high pressure to be increased, and is rapidly completed ester exchange reaction；
Preparation process 3）In described piston compressor, setting cellular solid acid catalyst plate, is that cellular porous solid acid is urged
Agent plate, by cordierite powder after the sulfuric acid solution of 15-50wt% soaks 24 hours at 50-60 DEG C, and drying is supported on
Porous plate is formed.
2. a kind of method preparing biodiesel according to claim 1, is characterized in that：Preparation process 1）Described is short
Chain alcohol is C1-C4 alcohol.
3. a kind of method preparing biodiesel according to claim 1, is characterized in that：Preparation process 1）Described work
Agent is from one of stearic acid, neopelex, lecithin, betaine type activating agent.
4. a kind of method preparing biodiesel according to claim 1, is characterized in that：Preparation process 2）Described oil
Fat is linseed oil, soybean oil, rubber seed oil, castor oil, cottonseed oil, rapeseed oil, or the kitchen waste oil from preliminary refining process,
Animal oil.
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| CN100448946C (en) * | 2006-07-10 | 2009-01-07 | 中国科学院广州能源研究所 | Method for conitinuously producing biological diesel oil using solid acid catalyst and piston flow reactor |
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