CN113583724A - Efficient green continuous preparation method of biodiesel - Google Patents
Efficient green continuous preparation method of biodiesel Download PDFInfo
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- CN113583724A CN113583724A CN202010364907.1A CN202010364907A CN113583724A CN 113583724 A CN113583724 A CN 113583724A CN 202010364907 A CN202010364907 A CN 202010364907A CN 113583724 A CN113583724 A CN 113583724A
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- 230000003197 catalytic effect Effects 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 36
- 239000000194 fatty acid Substances 0.000 claims abstract description 36
- 229930195729 fatty acid Natural products 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000005886 esterification reaction Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 239000006184 cosolvent Substances 0.000 claims abstract description 17
- 230000032050 esterification Effects 0.000 claims abstract description 12
- 239000010775 animal oil Substances 0.000 claims abstract description 6
- 239000010773 plant oil Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 28
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 23
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- 239000011148 porous material Substances 0.000 claims description 7
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 6
- 235000019737 Animal fat Nutrition 0.000 claims description 5
- 239000008158 vegetable oil Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 235000019197 fats Nutrition 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000011973 solid acid Substances 0.000 claims description 3
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
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- 125000005456 glyceride group Chemical group 0.000 description 16
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- 235000021588 free fatty acids Nutrition 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- -1 oleum Rapae Substances 0.000 description 7
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
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- 230000001502 supplementing effect Effects 0.000 description 3
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- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 235000019871 vegetable fat Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
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- 241001465754 Metazoa Species 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 239000002285 corn oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
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- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for efficiently, greenly and continuously preparing biodiesel, and aims to solve the technical problems of complex process, difficult control, more side reactions, more emulsions, serious pollution caused by waste acid and alkali generated in the separation process, low catalytic efficiency and difficult reutilization of a catalyst in the prior art. The method comprises the following steps: adding low-carbon alkanol into plant and/or animal oil; carrying out esterification reaction in an acid membrane reactor; the obtained esterification product flows into a membrane separator to separate fatty acid low-carbon alkanol monoester, and unreacted raw materials are recovered; adding a lower alkanol and a cosolvent; performing ester exchange reaction in an alkali membrane reactor; and (4) allowing the ester exchange product to flow into a membrane separator to separate fatty acid lower alkanol monoester. The method has simple process, easy control, continuous production, easy process amplification and industrial production; the corrosion to equipment is small, and the environment is friendly; can save cost and reduce labor intensity, and has wide industrial application value.
Description
Technical Field
The invention relates to the technical field of biological energy, in particular to a method for efficiently, greenly and continuously preparing biodiesel.
Background
The biodiesel oil is fatty acid methyl ester or ethyl ester prepared by ester-converting vegetable oil (such as oleum Rapae, soybean oil, peanut oil, corn oil, cottonseed oil, etc.), animal oil (such as fish oil, lard, beef tallow, mutton fat, etc.), waste oil or microbial oil with methanol or ethanol. Biodiesel is a typical 'green energy source', and has the characteristics of good environmental protection performance, good engine starting performance, good fuel performance, wide raw material source, renewability and the like.
At present, the production and preparation of biodiesel comprise a physical method, a chemical catalysis method, a biological catalysis method and a supercritical esterification/ester exchange reaction method without a catalyst. Physical method moderates vegetable oil and solvent to prepare microemulsion, which can improve physical and chemical properties, but is easy to produce emulsion breaking phenomenon and has very limited application; the biological catalysis method adopts lipase to catalyze the ester exchange reaction of alcohol and fabric, although the reaction condition is mild and the specificity is good, the cost of the enzyme is high, the enzyme is volatile and active, the reaction time is long, and the industrial application is difficult; the supercritical method has high reaction speed, high conversion rate and high product purity, but in order to control the operation parameters of the ester exchange reaction, the critical parameters of a methanol-grease mixing system need to be determined in the production. Because the critical parameters are difficult to measure in experiments under the conditions of high temperature and high pressure, the estimation has large error and is only applied in laboratories; the chemical catalysis method is mostly adopted in the production, including homogeneous catalysis and heterogeneous catalysis, but the problems of complex process, difficult control, more side reactions, more emulsions, serious waste acid and alkali generation in the separation process, serious pollution, low catalysis efficiency, difficult reutilization of the catalyst and the like exist.
Disclosure of Invention
The invention aims to provide a method for efficiently, greenly and continuously preparing biodiesel. The method aims to solve the problems that the prior art is complex in process, difficult to control, high in side reaction and emulsion, serious in pollution due to waste acid and alkali generated in the separation process, low in catalytic efficiency, difficult to recycle the catalyst and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
the method for preparing the biodiesel in an efficient green continuous manner comprises the following steps:
(1) adding low-carbon alkanol into vegetable and/or animal oil and fat, and preheating to obtain homogeneous reaction liquid 1;
(2) carrying out esterification reaction on the obtained homogeneous reaction liquid 1 in an acid membrane reactor to obtain an esterification product;
(3) the obtained esterification product flows into a membrane separator to separate fatty acid low-carbon alkanol monoester, and unreacted raw materials are recovered;
(4) taking the unreacted raw materials, adding low-carbon alkanol and cosolvent, and preheating again to obtain homogeneous reaction liquid 2;
(5) carrying out ester exchange reaction on the obtained homogeneous reaction liquid 2 in an alkali membrane reactor to obtain an ester exchange product;
(6) and (4) allowing the ester exchange product to flow into a membrane separator to separate fatty acid lower alkanol monoester.
The other efficient green continuous preparation method of the biodiesel comprises the following steps:
(1) adding plant and/or animal oil into a raw material tank, adding low-carbon alkanol, and preheating to obtain homogeneous reaction liquid 1;
(2) pumping the obtained homogeneous reaction liquid 1 into an acid membrane reactor for esterification reaction to obtain an esterification product;
(3) continuously flowing the obtained esterification product into a first membrane separator to separate fatty acid low-carbon alkanol monoester, storing the fatty acid low-carbon alkanol monoester in a first product tank, and recycling unreacted raw materials to enter an intermediate tank;
(4) adding low-carbon alkanol and cosolvent into the intermediate tank, and preheating again to obtain homogeneous reaction liquid 2;
(5) pumping the obtained homogeneous reaction liquid 2 into an alkali membrane reactor for ester exchange reaction to obtain an ester exchange product;
(6) and continuously flowing the ester exchange product into a second membrane separator to separate fatty acid low-carbon alkanol monoester, storing the fatty acid low-carbon alkanol monoester into a second product tank, and separating and storing a byproduct into a byproduct tank to obtain the product.
Preferably, in the step (1), the vegetable and/or animal fat or oil: the mass ratio of the low-carbon alkanol is 4-6: 1; the preheating temperature is 60-65 ℃.
Preferably, in the step (2), the catalytic membrane of the acid membrane reactor is a polymer catalytic membrane with acid groups or a polymer catalytic membrane loaded with solid acid and/or heteropoly acid;
the polymer is at least one of polyethylene-vinyl alcohol, polyvinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, cellulose, polysulfone, polyether sulfone, polyether ether ketone and chitosan;
the polymer catalytic membrane is an acidic catalytic membrane prepared from any one of sulfonated polyvinyl alcohol, sulfonated polysulfone, sulfonated polyether-ether-ketone, phosphatized polyvinyl alcohol, zirconium sulfate loaded polyvinyl alcohol and phosphotungstic acid loaded polyether sulfone.
Preferably, in the step (2), the space velocity of the material reactor for the esterification reaction is 0.01min-1～0.3h-1And the reaction temperature is 50-70 ℃.
Preferably, in the step (3), the separation membrane in the membrane separator is made of any high polymer of polyethylene-vinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, cellulose, polysulfone or polyethersulfone, and chitosan; the average pore diameter of the separation membrane is 1-100 microns, and the porosity is 10-80%.
Preferably, in the step (5), the catalytic membrane of the alkali membrane reactor is a polymer catalytic membrane with basic groups or a polymer catalytic membrane loaded with solid alkali;
the polymer is at least one of polyethylene-vinyl alcohol, polyvinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, cellulose, polysulfone, polyether sulfone, polyether ether ketone and chitosan; .
The polymer catalytic membrane is an alkaline catalytic membrane prepared from any one of guanidino polyvinyl alcohol, guanidino chitosan, quaternized polyether sulfone and quaternized polysulfone.
Preferably, in the step (4), the unreacted raw materials: low-carbon alkanol: the mass ratio of the cosolvent is 1.6-9: 2-10: 1; the temperature of the secondary preheating is 40-60 ℃.
Preferably, in the step (2), the space velocity of the material reactor for the transesterification reaction is 0.08min-1～0.2h-1And the reaction temperature is 40-60 ℃.
Preferably, in the step (6), the separation membrane in the membrane separator is made of any high polymer of polyethylene-vinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, cellulose, polysulfone or polyethersulfone, and chitosan; the average pore diameter of the separation membrane is 1-100 microns, and the porosity is 10-80%.
Compared with the prior art, the invention has the main beneficial technical effects that:
(1) the method of the invention integrates the catalytic membrane as the catalyst and the acid and alkali membrane reactors to realize the continuous preparation method of the biodiesel, realizes the dual functions of membrane catalysis and membrane separation products, and can be further applied to the relevant esterification reaction and ester exchange reaction of organic carboxylic ester.
(2) The membrane catalysis mechanism of the membrane reactor device is mainly that mass transfer is carried out in membrane holes by means of pressure flow convection, so that reactants can reach a catalytic activity center more easily, and further the reaction rate and the catalytic performance are further improved. Because the catalytic particles are fixed in the membrane pore channel, the problems of low catalytic efficiency, difficult reutilization of the catalyst, even product pollution and the like in the traditional process are solved; the membrane separator device can effectively separate reactants and products and has high separation rate. Solves the problems of difficult product separation in the traditional process, and avoids the problems of waste acid, alkali liquor and the like generated in the separation process.
(3) The method has simple process, easy control, continuous production, easy process amplification and industrialized production; the corrosion to equipment is small, and the environment is friendly; the glycerol which is a byproduct of the process can be applied to various purposes such as daily chemicals, foods, industries and the like; the cost is obviously saved, the labor intensity is reduced, and the method has important academic value and wide industrial application value.
Drawings
FIG. 1 is a flow chart illustrating the present invention.
FIG. 2 is a schematic flow chart of the preparation process of the examples.
In the above fig. 2, 1 is a raw material tank, 2 is a peristaltic pump, 3 is an acid membrane reactor, 4 is a first separator, 5 is a first product tank, 6 is a make-up tank, 7 is an intermediate tank, 8 is an alkali membrane reactor, 9 is a second separator, 10 is a second product tank, and 11 is a byproduct tank.
Detailed Description
The following examples are intended to illustrate the present invention in detail and should not be construed as limiting the scope of the present invention in any way.
The instruments and devices referred to in the following examples are conventional instruments and devices unless otherwise specified; the related reagents are all conventional reagents in the market, if not specifically indicated; the test methods involved are conventional methods unless otherwise specified.
Example (b): method for efficiently, green and continuously preparing biodiesel
As shown in figure 1, the method takes animal and vegetable fat (containing free fatty acid and fatty glyceride) as raw materials and comprises the following steps:
(1) taking raw materials and low-carbon alkanol, and preheating the raw materials and the low-carbon alkanol into homogeneous reaction liquid;
(2) pumping the mixture into an acid film reactor by a peristaltic pump to perform continuous esterification reaction, and reacting free fatty acid in the raw material with low-carbon alkanol to generate fatty acid low-carbon alkanol monoester and water;
the acid film reactor is provided with a catalytic film which is a polymer catalytic film with sulfonic acid groups, phosphoric acid groups or other acid groups or a polymer catalytic film loaded with solid acid and heteropoly acid;
the polymer is polyethylene-vinyl alcohol, polyvinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, various celluloses, polysulfone or polyethersulfone, polyetheretherketone, chitosan, etc.
The polymer catalytic membrane is an acidic catalytic membrane prepared from sulfonated polyvinyl alcohol, sulfonated polysulfone, sulfonated polyether-ether-ketone, phosphatized polyvinyl alcohol, zirconium sulfate loaded polyvinyl alcohol, phosphotungstic acid loaded polyether sulfone and the like;
(3) the mixture flows into a membrane separator to separate the esterification product (oil-water separation), fatty acid low-carbon alkanol monoester and water are separated, and fatty acid low-carbon alkanol monoester, namely biodiesel, is obtained after water is removed by reduced pressure distillation; recovering the unreacted raw material (fatty glyceride);
the separation membrane in the membrane separator is made of high polymers such as polyethylene-vinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, various celluloses, (sulfonated) polysulfone or (sulfonated) polyethersulfone, chitosan and the like, the average pore diameter is 1-100 micrometers, and the porosity is 10-80%.
(4) Taking and recycling unreacted raw materials (fatty glyceride), low-carbon alkanol and cosolvent, and preheating the raw materials, the low-carbon alkanol and the cosolvent into homogeneous reaction liquid;
(5) pumping the mixture into an alkali membrane reactor by a peristaltic pump to perform ester exchange reaction, and reacting the fatty acid glyceride with low-carbon alkanol to generate fatty acid low-carbon alkanol monoester and glycerol;
the alkali membrane reactor is provided with a catalytic membrane which is a polymer catalytic membrane with quaternary ammonium groups, guanidino groups or other basic groups or a polymer catalytic membrane loaded with solid alkali.
The polymer is polyethylene-vinyl alcohol, polyvinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, various celluloses, polysulfone or polyethersulfone, polyetheretherketone, chitosan, etc.
The polymer catalytic membrane is an alkaline catalytic membrane prepared from guanidino polyvinyl alcohol, guanidino chitosan, quaternized polyether sulfone, quaternized polysulfone and the like.
(6) The mixture flows into a membrane separator to separate the ester exchange product (glycerin, oil and water), so as to separate fatty acid lower alkanol monoester and water, and the fatty acid lower alkanol monoester, namely the biodiesel, is obtained after the water is removed by reduced pressure distillation. The glycerin can be recovered after separation, and other chemical fields can be used after the glycerin is completely recovered.
The separation membrane in the membrane separator is made of high polymers such as polyethylene-vinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, various celluloses, (sulfonated) polysulfone or (sulfonated) polyethersulfone, chitosan and the like, the average pore diameter is 1-100 micrometers, and the porosity is 10-80%.
Test example 1: method for efficiently, green and continuously preparing biodiesel
As shown in fig. 2, the specific steps are as follows:
(1) 600 g of vegetable oil (wherein free fatty acid accounts for 10% of the total weight, and fatty glyceride accounts for 90% of the total weight) is put into a raw material tank 1;
(2) then adding 100 g of methanol, uniformly stirring, and preheating to 64 ℃;
(3) the reaction mixture is added into an acid membrane reactor 3 filled with a phosphotungstic acid/polyvinyl alcohol catalytic membrane through a peristaltic pump 2 for continuous esterification reaction, and the airspeed of the material reactor is 0.01h-1Carrying out esterification reaction on free fatty acid and methanol at the reaction temperature of 64 ℃ to obtain fatty acid methyl ester and water;
(4) continuously flowing out the product fatty acid methyl ester, water and unreacted raw materials (fatty glyceride) into a first separator 4 (the separation membrane is a polysulfone membrane), distilling the product fatty acid methyl ester and water under reduced pressure to remove water to obtain fatty acid low-carbon alkanol monoester (biodiesel) and storing the fatty acid low-carbon alkanol monoester (biodiesel) in a first product tank 5;
(5) recovering unreacted raw materials (containing fatty glyceride and a small amount of methanol, wherein the methanol and the fatty glyceride are insoluble and layered) into an intermediate tank 7, adding 600 g of methanol and 60 g of cosolvent n-hexane stored in a material supplementing tank 6, and preheating to 60 ℃;
(6) pumping the mixture into an alkali membrane reactor 8 provided with a guanidyl grafted polyvinyl alcohol catalytic membrane through a peristaltic pump 2 for continuous ester exchange reaction, wherein the space velocity of the material reactor is 0.05h-1Carrying out ester exchange reaction on fatty glyceride and methanol at the reaction temperature of 60 ℃ to obtain fatty methyl ester and glycerol;
(7) the product fatty acid methyl ester, glycerol, methanol and cosolvent normal hexane continuously flow out and enter a second separator 9 (a separation membrane is a polyvinylidene fluoride membrane), fatty acid methyl ester, namely biodiesel, is separated and stored in a second product tank 10; the glycerin, the methanol and the cosolvent normal hexane are subjected to reduced pressure distillation to remove the methanol and the cosolvent normal hexane, and the byproduct glycerin is separated and stored in a byproduct tank 11.
The conversion rate of esterification reaction obtained by acid-base titration method was 98.4%, and the conversion rate of ester exchange reaction obtained by nuclear magnetic resonance method was 95.3%.
Test example 2: method for efficiently, green and continuously preparing biodiesel
As shown in fig. 2, the specific steps are as follows:
(1) placing 800 g of animal fat (wherein free fatty acid accounts for 50% of the total weight, and fatty glyceride accounts for 50% of the total weight) into a raw material tank 1;
(2) adding 200 g of ethanol, uniformly stirring, and preheating to 60 ℃;
(3) the reaction mixture is added into an acid membrane reactor 3 filled with a phosphotungstic acid/polyvinyl alcohol catalytic membrane through a peristaltic pump 2 for continuous esterification reaction, and the airspeed of the material reactor is 0.03h-1Carrying out esterification reaction on free fatty acid and ethanol at the reaction temperature of 50 ℃ to obtain fatty acid ethyl ester and water;
(4) the product fatty acid ethyl ester, water and unreacted raw materials (fatty glyceride) continuously flow out to enter a first separator 4 (the separation membrane is a polyether sulfone membrane), the product fatty acid ethyl ester and water are subjected to reduced pressure distillation to remove water, and then fatty acid low-carbon alkanol monoester (biodiesel) is obtained and stored in a first product tank 5;
(5) recovering unreacted raw materials (fatty glyceride) into an intermediate tank 7, adding 1000 g of ethanol and 100 g of cosolvent tetrahydrofuran stored in a material supplementing tank 6, and preheating to 52 ℃;
(6) pumping the mixture into an alkali membrane reactor 8 provided with a guanidino polyvinyl alcohol catalytic membrane through a peristaltic pump 2 for continuous ester exchange reaction, wherein the space velocity of the material reactor is 0.02h-1Carrying out ester exchange reaction on fatty glyceride and ethanol at the reaction temperature of 50 ℃ to obtain fatty ethyl ester and glycerol;
(7) the product fatty acid ethyl ester, glycerol, ethanol and cosolvent tetrahydrofuran continuously flow out and enter a second separator 9 (a separation membrane is a polyethylene-vinyl alcohol membrane), fatty acid ethyl ester, namely biodiesel is separated out and stored in a second product tank 10; the by-product is separated and stored in a by-product tank 11.
The conversion rate of esterification reaction obtained by acid-base titration method was 97.8%, and the conversion rate of ester exchange reaction obtained by nuclear magnetic resonance method was 94.2%.
Test example 3: method for efficiently, green and continuously preparing biodiesel
As shown in fig. 2, the specific steps are as follows:
(1) placing 400 g of animal fat (wherein free fatty acid accounts for 80% of the total weight, and fatty glyceride accounts for 20% of the total weight) into a stock tank 1;
(2) adding 80 g of propanol, uniformly stirring, and preheating to 65 ℃;
(3) the reaction mixture is added into an acid membrane reactor 3 filled with a phosphotungstic acid/polyvinyl alcohol catalytic membrane through a peristaltic pump 2 for continuous esterification reaction, and the airspeed of the material reactor is 0.01h-1Carrying out esterification reaction on free fatty acid and propanol at the reaction temperature of 67 ℃ to obtain fatty acid propyl ester and water;
(4) continuously flowing out the product of the propyl fatty acid ester, water and unreacted raw materials (fatty glyceride) into a first separator 4 (a separation membrane is a sulfonated polyether sulfone membrane), distilling the product of the propyl fatty acid ester and the water under reduced pressure to remove the water to obtain fatty acid lower alkanol monoester (biodiesel) and storing the fatty acid lower alkanol monoester (biodiesel) in a first product tank 5;
(5) recovering unreacted raw materials (fatty glyceride) into an intermediate tank 7, adding 100 g of propylene alcohol and 50 g of cosolvent n-hexane stored in a material supplementing tank 6, and preheating to 45 ℃;
(6) pumping the mixture into an alkali membrane reactor 8 filled with quaternary ammonium polysulfone catalytic membrane through a peristaltic pump 2 for continuous ester exchange reaction, wherein the space velocity of the material reactor is 0.08h-1Carrying out ester exchange reaction on fatty glyceride and propanol at the reaction temperature of 43 ℃ to obtain fatty propyl ester and glycerol;
(7) the product of the propyl fatty acid ester, the glycerol, the propanol and the cosolvent normal hexane continuously flow out to enter a second separator 9 (the separation membrane is a sulfonated polysulfone membrane), the propyl fatty acid ester, namely the biodiesel, is separated and stored in a second product tank 10; the by-product is separated and stored in a by-product tank 11.
The conversion rate of esterification reaction obtained by acid-base titration method was 98.7%, and the conversion rate of ester exchange reaction obtained by nuclear magnetic resonance method was 97.5%.
While the invention has been described in detail with reference to the drawings and examples, it will be understood by those skilled in the art that various changes in the specific parameters and equivalents of the ingredients thereof may be made therein without departing from the spirit of the invention, and thus, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
Claims (10)
1. The method for efficiently and continuously preparing the biodiesel in a green way is characterized by comprising the following steps of:
(1) adding low-carbon alkanol into vegetable and/or animal oil and fat, and preheating to obtain homogeneous reaction liquid 1;
(2) carrying out esterification reaction on the obtained homogeneous reaction liquid 1 in an acid membrane reactor to obtain an esterification product;
(3) the obtained esterification product flows into a membrane separator to separate fatty acid low-carbon alkanol monoester, and unreacted raw materials are recovered;
(4) taking the unreacted raw materials, adding low-carbon alkanol and cosolvent, and preheating again to obtain homogeneous reaction liquid 2;
(5) carrying out ester exchange reaction on the obtained homogeneous reaction liquid 2 in an alkali membrane reactor to obtain an ester exchange product;
(6) and (4) allowing the ester exchange product to flow into a membrane separator to separate fatty acid lower alkanol monoester.
2. The method for efficiently and continuously preparing the biodiesel in a green way is characterized by comprising the following steps of:
(1) adding plant and/or animal oil into a raw material tank, adding low-carbon alkanol, and preheating to obtain homogeneous reaction liquid 1;
(2) pumping the obtained homogeneous reaction liquid 1 into an acid membrane reactor for esterification reaction to obtain an esterification product;
(3) continuously flowing the obtained esterification product into a first membrane separator to separate fatty acid low-carbon alkanol monoester, storing the fatty acid low-carbon alkanol monoester in a first product tank, and recycling unreacted raw materials to enter an intermediate tank;
(4) adding low-carbon alkanol and cosolvent into the intermediate tank, and preheating again to obtain homogeneous reaction liquid 2;
(5) pumping the obtained homogeneous reaction liquid 2 into an alkali membrane reactor for ester exchange reaction to obtain an ester exchange product;
(6) and continuously flowing the ester exchange product into a second membrane separator to separate fatty acid low-carbon alkanol monoester, storing the fatty acid low-carbon alkanol monoester into a second product tank, and separating and storing a byproduct into a byproduct tank to obtain the product.
3. The efficient green continuous biodiesel production method according to claim 1 or claim 2, wherein in the step (1), the plant and/or animal fat/oil: the mass ratio of the low-carbon alkanol is 4-6: 1; the preheating temperature is 60-65 ℃.
4. The efficient green continuous biodiesel production method according to claim 1 or claim 2, wherein in the step (2), the catalytic membrane of the acid membrane reactor is a polymer catalytic membrane with acidic groups or a polymer catalytic membrane loaded with solid acids and/or heteropoly acids;
the polymer is at least one of polyethylene-vinyl alcohol, polyvinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, cellulose, polysulfone, polyether sulfone, polyether ether ketone and chitosan;
the polymer catalytic membrane is an acidic catalytic membrane prepared from any one of sulfonated polyvinyl alcohol, sulfonated polysulfone, sulfonated polyether-ether-ketone, phosphatized polyvinyl alcohol, zirconium sulfate loaded polyvinyl alcohol and phosphotungstic acid loaded polyether sulfone.
5. The efficient green continuous biodiesel production method according to claim 1 or claim 2, wherein in the step (2), the space velocity of the esterification feed reactor is 0.01min-1～0.3h-1And the reaction temperature is 50-70 ℃.
6. The efficient green continuous preparation method of biodiesel according to claim 1 or claim 2, wherein in the step (3), the separation membrane in the membrane separator is made of any one of polyethylene-vinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, cellulose, polysulfone or polyether sulfone, and chitosan; the average pore diameter of the separation membrane is 1-100 microns, and the porosity is 10-80%.
7. The efficient green continuous biodiesel production method according to claim 1 or claim 2, wherein in the step (5), the alkali membrane reactor is provided with a catalytic membrane which is a polymer catalytic membrane with basic groups or a polymer catalytic membrane loaded with solid alkali;
the polymer is at least one of polyethylene-vinyl alcohol, polyvinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, cellulose, polysulfone, polyether sulfone, polyether ether ketone and chitosan;
the polymer catalytic membrane is an alkaline catalytic membrane prepared from any one of guanidino polyvinyl alcohol, guanidino chitosan, quaternized polyether sulfone and quaternized polysulfone.
8. The efficient green continuous biodiesel production method according to claim 1 or claim 2, wherein in the step (4), the unreacted raw material: low-carbon alkanol: the mass ratio of the cosolvent is 1.6-9: 2-10: 1; the temperature of the secondary preheating is 40-60 ℃.
9. The efficient green continuous biodiesel production method according to claim 1 or claim 2, wherein in the step (5), the space velocity of the transesterification feed reactor is 0.08min-1～0.2h-1And the reaction temperature is 40-60 ℃.
10. The efficient green continuous preparation method of biodiesel according to claim 1 or claim 2, wherein in the step (6), the separation membrane in the membrane separator is made of any one of polyethylene-vinyl alcohol, polyvinylidene fluoride, polyacrylonitrile, cellulose, polysulfone or polyether sulfone, and chitosan; the average pore diameter of the separation membrane is 1-100 microns, and the porosity is 10-80%.
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