CN104745310A - Method for producing biodiesel by adopting microchannel reactor - Google Patents
Method for producing biodiesel by adopting microchannel reactor Download PDFInfo
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- 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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a method for producing biodiesel by adopting a microchannel reactor, belonging to the technical field of green renewable energy resources. The method is a novel technology for producing biodiesel products, and in the high-flux continuous-flow microchannel reactor, renewable energy resources such as animal and vegetable oil, waste oil and refined oil as well as methyl alcohol are taken as raw materials, and are subjected to transesterification in the microchannel reactor for a short reaction time of dozens of seconds or several minutes under the catalysis of alkali or acid to produce a biodiesel product. The materials enter the continuous-flow microchannel reactor through a metering pump, and are preheated, mixed and subjected to aftertreatment in a transesterification module to obtain the biodiesel product. The method has the advantages that the operation is simple and safe, and the biodiesel product can be continuously produced with a high yield, and besides, the environment pollution caused by the technology is greatly lowered.
Description
Technical field
The invention belongs to technical field of green regenerative energy sources, be specifically related to the renewable resourcess such as propagation waste oil fat, acidification oil, sewer oil and concise grease and methyl alcohol as raw material, under the katalysis of alkali or acid, in Continuous Flow micro passage reaction, carry out transesterification reaction production biodiesel oil product.
Background technology
Biofuel and fatty acid methyl ester are oil-fired a kind of good substitutes.The reproducible environment-friendly type energy of one that biofuel mainly utilizes animal and vegetable oil or waste oil, refining oil to make as raw material and industrial raw material.Biofuel, with the recyclability of its uniqueness and green environmental protection, becomes a kind of petroleum diesel substitute of high-quality, is considered to solve global energy crisis, environmental stress of releiving, control one of optimal approach of topsoil.
Method at present for the production of biofuel can be divided into physical method, chemical process and biological method three kinds.
Physical method: the method preparing biofuel is that grease is used in combination according to different ratios from petrifaction diesel, its dynamic performance and excess load performance is good, thermo-efficiency is high, but its result makes us not satisfied.But because general grease is higher than the viscosity of petrifaction diesel, the biofuel that such method is formed there will be a series of problems being unfavorable for using such as the series of problems such as coking and lubricating oil dilution and occurs in the process of burning.Although direct mixing method technique is simple, the shortcomings such as but the biodiesel fuel quality prepared is poor, stability is low, and can not inherently change the physico-chemical properties such as plant oil viscosity, the biofuel that therefore direct mixing method is produced can not use for a long time on a diesel engine.
Chemical method: animal-plant oil is changed its molecular structure and carry out chemical conversion, lipid acid three ester is made to change the fatty acid methyl ester of strand into, thus make it have the character similar with petrifaction diesel, can directly use as the fuel of engine, having of high temperature pyrolytic cracking is simple to operate, to advantages such as raw material can make full use of, because its production technique program is complicated, equipment requirements is high, but due to its biodiesel production rate low, be not therefore widely used in industrial production.Ester-interchange method refers under the condition of normal temperature and pressure, under the catalyst effects such as acid, alkali, enzyme, or under postcritical condition (namely not using any catalyzer), the short chain alcohol such as triglyceride level and methanol/ethanol is made to carry out the method for transesterification reaction generation biofuel.
Biological method mainly utilizes lipase-catalyzed grease esterification to prepare biofuel.Relative to traditional acid-base catalysis, lipase-catalyzed preparation biofuel is lower to environmental requirement, under normal temperature and pressure conditions; Alcohol consumption is less, and catalyzer lipase and reaction product are not dissolved each other, easily the advantage such as removing, therefore, utilizes lipase-catalyzed preparing biodiesel from lipid to become emphasis in biofuel preparation research.
Patent CN1580190A reports a kind of under solid acidand basecatalysts exists, and utilizes the transesterification reaction of soybean oil and methyl alcohol to obtain biofuel.Reaction terminates first to be separated from reaction soln by catalyzer with whizzer afterwards, obtains the method for biofuel through stratification, distillation.Patent 101074389A provides the method that one utilizes waste animal and plant (sewer oil) production biofuel, by waste animal vegetable oil and methanol mixed, react under the katalysis of alkali or acid, cooling, separation obtains coarse biodiesel, with rear, filtering and impurity removing in utilization acid or alkali, steam unnecessary methyl alcohol and namely obtain biofuel.Patent CN 103215140 A discloses a kind of method of catalyst-free continuously producing biodiesel.The method adopts the heating and pressurizing such as waste animal and vegetable oil, microbial oil to react with methyl alcohol generation fat hydrolysis, fatty acid esterification and glyceride transesterification in biofuel reaction tower, and reaction product is squeezed into continuously in glycerol distillation tower, methyl esters deodorizing tower and methyl ester distilled tower and namely obtain biofuel.This method can realize that serialization, speed of response are fast, low production cost, simple to operate and be reliably applicable to scale operation without processing wastewater, steady quality.Patent CN 103695484 A discloses the method with Biodiesel Production by Lipase-catalysis, relates to the synthetic method of biofuel.Be in the petroleum ether system of 28-44 DEG C in temperature, add oleic acid and methyl alcohol that mol ratio is 1:0.8-1.4, mass percent is the immobilized lipase of 5%, and the reaction times is 24h.Adopt the candiyeast of immobilized lipase as biological catalyst, have developed the technique of a set of new enzymatic esterification technique synthetic fatty acid acyl ester.
Existing document and Patents inquiry, in production of biodiesel process, major part is all adopt autoclave periodical operation, up to now, there is not yet the research of the method for carrying out transesterify production biofuel in the mode of microchannel Continuous Flow.The invention provides a kind of in micro passage reaction with the operational path of the mode catalytic transesterification production biofuel of Continuous Flow.
When carrying out synthetic reaction condition screening in early stage in micro passage reaction, need reactant consumption very micro-, not only can reduce the consumption of costliness, poisonous, adverse reaction thing, the environmental pollutant produced in reaction process are also few, laboratory is substantially pollution-free, is the technology platform of a kind of environmental friendliness, study on the synthesis novel substance.Obtain in micro passage reaction product and modern age analytical instrument, as GC, GC-MS, HPLC and NMR carry out the matching analysis, make modern age analytical instrument can be used for direct-on-line monitoring and react the degree of carrying out, substantially increase the speed of research synthetic route.
The type of the special glass functional module of micro passage reaction has straight-through channel type, cardioid hybrid junctions configuration, connects straight-through channel type after having one section of cardioid mixed structure, connect after having one section of kapillary mixed structure straight-through channel type etc.The special glass functional module of micro passage reaction has two functional module of opening for feed list discharge port and the functional module of single opening for feed and single discharge port.Its safe operating temperature range of micro passage reaction is-25 DEG C ~ 200 DEG C, and safe working pressure scope is 0 ~ 18bar, and material pipeline connects for PFA(perfluoroalkoxy resin) material.European patent WO2010/037012A2 is the module patent about special construction design, the structure of special module has been write out in detail in patent, the size of module and the arrangement of passage etc., indicate module integrated and microminiaturized be that chemical process amplifies safer selection.
Summary of the invention
The object of the invention be to provide a kind of in micro passage reaction with the mode transesterify production biodiesel oil product of Continuous Flow, compared with existing technique, this technique has reaction conditions and accurately controls, reduce the discharge of organic liquid waste, continuous safe mode is produced, and Exchange Ester Process is completed within the extremely short time, esterification yield is high, and biofuel yield is high.
The present invention is a kind of method adopting micro passage reaction production biofuel, it is characterized in that carrying out according to following step:
(1) with waste oil (renewable resources such as propagation waste oil fat, acidification oil, sewer oil and concise grease) and methyl alcohol for raw material, under the katalysis of alkali or acid, in Continuous Flow micro passage reaction, carry out transesterification reaction production biodiesel oil product.
Under agitation alkali or acid catalyst are dissolved in methyl alcohol and are made into methanol solution and waste oil is raw material, pass into respectively in micro passage reaction through volume pump and carry out preheating in each channel module, design temperature is controlled by external heat exchanger, and heat transferring medium is thermal oil; Waste oil is changed again: methanol solution mol ratio=1:4 ~ 1:10 by flow control; Control waste oil flow velocity: 1mL/min ~ 5mL/min, control methanol solution flow velocity: 10mL/min ~ 20mL/min; Synchronously enter in mass transfer enhancement pattern block via respective volume pump and carry out hybrid reaction, mixing temperature is controlled by external heat exchanger equally;
(2) by the mol ratio of flow control waste oil and methanol solution, in this module after the raw reaction of hybrid concurrency, continue through a series of mass transfer enhancement type microchannel module and once-through type microchannel module, after esterification, ester-exchange reaction complete, product flows out from the outlet of reactor, enters cooling last handling process; This reaction process reaction time in micro passage reaction is 50s ~ 100s, and temperature of reaction is 50 ~ 80 DEG C, and pressure is 0.1 ~ 1.5 MPa;
(3) micro passage reaction is exported the reaction solution obtained, refrigerated separation obtains coarse biodiesel, then by coarse biodiesel utilize acid or alkali in and after, filter out impurities, steam unnecessary methyl alcohol and namely obtain biofuel.Biodiesel oil product yield about 95 ~ 98%.
Wherein in step (1), waste oil is a kind of or several arbitrarily mixture in propagation waste oil fat, acidification oil, sewer oil, concise grease.
Wherein in step (1), methanol solution is that alkali or acid catalyst are dissolved in methyl alcohol formulated, and the add-on of described catalysis acid or alkali is 1 ~ 3% of waste oil weight.Wherein be preferably 2%.
Wherein waste oil in step (1): methanol solution mol ratio is preferably 1:6.
Wherein in step (1), catalysis alkali is one or more in sodium hydroxide, calcium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate.
Wherein in step (1), catalysis acid is one or more in sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, acetic acid.
Wherein in step (1), waste oil flow velocity is preferably: 2mL/min ~ 3mL/min, controls methanol solution flow velocity and is preferably: 14mL/min ~ 16mL/min.
Wherein in step (2), in micro passage reaction, reaction time is preferably 60s ~ 80s, and temperature of reaction is preferably 60 ~ 65 DEG C, and pressure is preferably 0.4 ~ 0.6 MPa.
Neutralization alkali described in step (3) is at least one in sodium hydroxide, calcium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and described neutralization acid is at least one in sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, acetic acid.Its add-on is 0.1 ~ 0.5% of coarse biodiesel weight.
What the present invention was used is high-throughput microchannel continuous flow reactor, this reactive system is formed by polylith module assembled, and intermodule can assembled in parallel or assembled in series, module by integrated to heat exchange path and reaction path with one, or only containing reaction path, and be immersed in temperature control heat-conducting medium.In heat exchange path or heat-conducting medium, be furnished with thermopair, can be used for the actual temperature measuring heat transferring medium or extraneous heat-conducting medium in heat exchange path.In heat exchange path or heat-conducting medium, be furnished with thermopair, can be used for the actual temperature measuring heat transferring medium or extraneous heat-conducting medium in heat exchange path.The material of this module is silicon single crystal, special glass, pottery, the stainless steel scribbling corrosion resistant coating or metal alloy, tetrafluoroethylene etc.Reactive system can be anticorrosion withstand voltage, and it is different and different that voltage endurance capability looks material.In module, Micro Channel Architecture is divided once-through type channel architecture and strengthens mixed type channel architecture two kinds, and once-through type passage is tubular structure, and strengthening mixed type channel architecture is heart-shaped structure, and passage hydraulic diameter is 0.5mm ~ 10mm.
The mass transfer enhancement type micro channel reactor system that the present invention carries out waste oil alkali or acid catalyzed esterification production biofuel comprises waste oil preheating, hybrid reaction, Exchange Ester Process three part, therefore need the reaction module of raw material preheating module, mixing module and some amount, concrete quantity is determined by reaction time.
The present invention has following principal feature compared with prior art:
1. the present invention adopts Continuous Flow micro passage reaction, and reaction times from traditional a few hours shorten to tens seconds to several minutes, significantly improve reaction efficiency.
2. because raw material mixes splendid in microchannel, in reaction process, temperature accurately controls, and proportioning raw materials accurately controls, and the yield of product significantly improves.
3. the micro passage reaction material used in the present invention is special glass, and the material of volume pump is tetrafluoroethylene and titanium, and excellent corrosion resistance, avoids the problem that etching apparatus in conventional reactor is serious.
4., in micro passage reaction, omnidistance from charging, preheating, mixing and reaction process is Continuous Flow reaction, non-wastewater discharge, without exhaust emission, avoid the leakage needing in Conventional batch reaction to occur in additional configuration device and transfer, Environmental Safety, production efficiency is high.
Accompanying drawing explanation
Fig. 1 is waste oil alkali of the present invention or acid catalyzed esterification production biodiesel oil product process flow sheet;
Fig. 2 is micro passage reaction module used in the present invention and structure iron: 1-straight channel functional module, 2-" cardioid " structure function module, 3-" cardioid " structural representation;
Fig. 3 is micro passage reaction schematic flow sheet used in the present invention: 1,2-head tank, 3,4-feedstock pump, 5,6-tensimeter, and 7-craspedodrome channel module, 8,9-strengthens mixing " cardioid " module, 10-product-collecting.
Embodiment
With reference to Fig. 1 technical process of the present invention, utilize the setting drawing of Fig. 3, according to following step: (1) first by the waste oil in 1,2 storage tanks and methanol solution respectively through 3,4 volume pumps, according to certain proportioning squeeze into straight channel module 7(straight passage structures see in Fig. 2 No. 1) carry out preheating, whole process is by 5,6 tensimeter inspection system pressure; (2) waste oil and methanol solution pass into again after preheating micro mixer heart-shaped mixing module 8(heart-shaped structure see in Fig. 22, No. 3) in mix; (3) raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts; (4) export the reaction solution obtained through micro passage reaction, refrigerated separation obtains coarse biodiesel, then by coarse biodiesel utilize acid or alkali in and after, filter out impurities, steam unnecessary methyl alcohol and namely obtain biodiesel oil product.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
embodiment 1
(1) equipment therefor: high-throughput micro passage reaction (craspedodrome channel module+cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures waste oil, methanol solution (add-on of catalysis sodium hydroxide is 1% of waste oil weight).Set the flow control change waste oil of each volume pump 3, pump 4: methanol solution mol ratio=1:4, control waste oil flow velocity: 1mL/min, control methanol solution flow velocity: 10mL/min, material is squeezed into respectively in each straight channel warm-up block, temperature of reaction of controlling well is 50 DEG C, and pressure is 0.1MPa; Waste oil and methanol solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 50s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution obtained is exported through micro passage reaction, refrigerated separation obtains coarse biodiesel, after being utilized by coarse biodiesel sulfuric acid (add-on is 0.1% of coarse biodiesel weight) to neutralize again, filter out impurities, steam unnecessary methyl alcohol and namely obtain biodiesel oil product.Product yield about 95%.
embodiment 2
(1) equipment therefor: high-throughput micro passage reaction (craspedodrome channel module+cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures waste oil, methanol solution (add-on of catalysis calcium hydroxide is 1.5% of waste oil weight).Set the flow control change waste oil of each volume pump 3, pump 4: methanol solution mol ratio=1:5, control waste oil flow velocity: 2mL/min, control methanol solution flow velocity: 10mL/min, material is squeezed into respectively in each straight channel warm-up block, temperature of reaction of controlling well is 55 DEG C, and pressure is 0.2MPa; Waste oil and methanol solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 60s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution obtained is exported through micro passage reaction, refrigerated separation obtains coarse biodiesel, after being utilized by coarse biodiesel hydrochloric acid (add-on is 0.2% of coarse biodiesel weight) to neutralize again, filter out impurities, steam unnecessary methyl alcohol and namely obtain biodiesel oil product.Product yield about 97%.
embodiment 3
(1) equipment therefor: high-throughput micro passage reaction (craspedodrome channel module+cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures waste oil, methanol solution (add-on of catalysis potassium hydroxide is 1.5% of waste oil weight).Set the flow control change waste oil of each volume pump 3, pump 4: methanol solution mol ratio=1:6, control waste oil flow velocity: 3mL/min, control methanol solution flow velocity: 12mL/min, material is squeezed into respectively in each straight channel warm-up block, temperature of reaction of controlling well is 60 DEG C, and pressure is 0.4MPa; Waste oil and methanol solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 70s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution obtained is exported through micro passage reaction, refrigerated separation obtains coarse biodiesel, after being utilized by coarse biodiesel sulfuric acid (add-on is 0.3% of coarse biodiesel weight) to neutralize again, filter out impurities, steam unnecessary methyl alcohol and namely obtain biodiesel oil product.Product yield about 98%.
embodiment 4
(1) equipment therefor: high-throughput micro passage reaction (craspedodrome channel module+cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures waste oil, methanol solution (add-on of catalysis sulfuric acid is 2% of waste oil weight).Set the flow control change waste oil of each volume pump 3, pump 4: methanol solution mol ratio=1:7, control waste oil flow velocity: 3mL/min, control methanol solution flow velocity: 14mL/min, material is squeezed into respectively in each straight channel warm-up block, temperature of reaction of controlling well is 65 DEG C, and pressure is 0.6MPa; Waste oil and methanol solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 80s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution obtained is exported through micro passage reaction, refrigerated separation obtains coarse biodiesel, after being utilized by coarse biodiesel sodium carbonate (add-on is 0.3% of coarse biodiesel weight) to neutralize again, filter out impurities, steam unnecessary methyl alcohol and namely obtain biodiesel oil product.Product yield about 97%.
embodiment 5
(1) equipment therefor: high-throughput micro passage reaction (craspedodrome channel module+cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures waste oil, methanol solution (add-on of catalysis hydrochloric acid is 2.5% of waste oil weight).Set the flow control change waste oil of each volume pump 3, pump 4: methanol solution mol ratio=1:8, control waste oil flow velocity: 4mL/min, control methanol solution flow velocity: 16mL/min, material is squeezed into respectively in each straight channel warm-up block, temperature of reaction of controlling well is 70 DEG C, and pressure is 0.8MPa; Waste oil and methanol solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 85s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution obtained is exported through micro passage reaction, refrigerated separation obtains coarse biodiesel, after being utilized by coarse biodiesel sodium hydroxide (add-on is 0.4% of coarse biodiesel weight) to neutralize again, filter out impurities, steam unnecessary methyl alcohol and namely obtain biodiesel oil product.Product yield about 96%.
embodiment 6
(1) equipment therefor: high-throughput micro passage reaction (craspedodrome channel module+cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures waste oil, methanol solution (add-on of catalysis phosphoric acid is 2.5% of waste oil weight).Set the flow control change waste oil of each volume pump 3, pump 4: methanol solution mol ratio=1:9, control waste oil flow velocity: 4mL/min, control methanol solution flow velocity: 18mL/min, material is squeezed into respectively in each straight channel warm-up block, temperature of reaction of controlling well is 75 DEG C, and pressure is 1.0MPa; Waste oil and methanol solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 90s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution obtained is exported through micro passage reaction, refrigerated separation obtains coarse biodiesel, after being utilized by coarse biodiesel potassium hydroxide (add-on is 0.4% of coarse biodiesel weight) to neutralize again, filter out impurities, steam unnecessary methyl alcohol and namely obtain biodiesel oil product.Product yield about 97%.
embodiment 7
(1) equipment therefor: high-throughput micro passage reaction (craspedodrome channel module+cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures waste oil, methanol solution (add-on of catalysis sodium hydroxide is 3% of waste oil weight).Set the flow control change waste oil of each volume pump 3, pump 4: methanol solution mol ratio=1:10, control waste oil flow velocity: 5mL/min, control methanol solution flow velocity: 20mL/min, material is squeezed into respectively in each straight channel warm-up block, temperature of reaction of controlling well is 80 DEG C, and pressure is 1.5MPa; Waste oil and methanol solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 100s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution obtained is exported through micro passage reaction, refrigerated separation obtains coarse biodiesel, after being utilized by coarse biodiesel acetic acid (add-on is 0.5% of coarse biodiesel weight) to neutralize again, filter out impurities, steam unnecessary methyl alcohol and namely obtain biodiesel oil product.Product yield about 96%.
Claims (9)
1. adopt a method for micro passage reaction production biofuel, it is characterized in that carrying out according to following step:
(1) with waste oil and methyl alcohol for raw material, under the katalysis of alkali or acid, in Continuous Flow micro passage reaction, carry out transesterification reaction production biodiesel oil product;
under agitation alkali or acid catalyst are dissolved in methyl alcohol and are made into methanol solution and waste oil is raw material, pass into respectively in micro passage reaction through volume pump and carry out preheating in each channel module, design temperature is controlled by external heat exchanger, and heat transferring medium is thermal oil; Waste oil is changed again: methanol solution mol ratio=1:4 ~ 1:10 by flow control; Control waste oil flow velocity: 1mL/min ~ 5mL/min, control methanol solution flow velocity: 10mL/min ~ 20mL/min; Synchronously enter in mass transfer enhancement pattern block via respective volume pump and carry out hybrid reaction, mixing temperature is controlled by external heat exchanger equally;
(2) by the mol ratio of flow control waste oil and methanol solution, in this module after the raw reaction of hybrid concurrency, continue through a series of mass transfer enhancement type microchannel module and once-through type microchannel module, after esterification, ester-exchange reaction complete, product flows out from the outlet of reactor, enters cooling last handling process; This reaction process reaction time in micro passage reaction is 50s ~ 100s, and temperature of reaction is 50 ~ 80 DEG C, and pressure is 0.1 ~ 1.5 MPa;
(3) micro passage reaction is exported the reaction solution obtained, refrigerated separation obtains coarse biodiesel, then by coarse biodiesel utilize acid or alkali in and after, filter out impurities, steam unnecessary methyl alcohol and namely obtain biofuel; Biodiesel oil product yield about 95 ~ 98%.
2. a kind of method adopting micro passage reaction production biofuel according to claim 1, is characterized in that wherein the middle waste oil of step (1) is a kind of or several arbitrarily mixture in propagation waste oil fat, acidification oil, sewer oil, concise grease.
3. a kind of method adopting micro passage reaction production biofuel according to claim 1, it is characterized in that wherein the middle methanol solution of step (1) is that alkali or acid catalyst are dissolved in methyl alcohol formulated, the add-on of described catalysis acid or alkali is 1 ~ 3% of waste oil weight, is wherein preferably 2%.
4. a kind of method adopting micro passage reaction production biofuel according to claim 1, is characterized in that the wherein middle waste oil of step (1): methanol solution mol ratio is preferably 1:6.
5. a kind of method adopting micro passage reaction production biofuel according to claim 1, is characterized in that catalysis alkali in wherein step (1) is one or more in sodium hydroxide, calcium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate.
6. a kind of method adopting micro passage reaction production biofuel according to claim 1, is characterized in that catalysis acid in wherein step (1) is one or more in sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, acetic acid.
7. a kind of method adopting micro passage reaction production biofuel according to claim 1, it is characterized in that wherein the middle waste oil flow velocity of step (1) is preferably: 2mL/min ~ 3mL/min, controls methanol solution flow velocity and be preferably: 14mL/min ~ 16mL/min.
8. a kind of method adopting micro passage reaction production biofuel according to claim 1, it is characterized in that wherein in step (2) in micro passage reaction reaction time be preferably 60s ~ 80s, temperature of reaction is preferably 60 ~ 65 DEG C, and pressure is preferably 0.4 ~ 0.6 MPa.
9. a kind of method adopting micro passage reaction production biofuel according to claim 1, it is characterized in that wherein neutralization alkali described in step (3) is at least one in sodium hydroxide, calcium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, described neutralization acid is at least one in sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, acetic acid, and its add-on is 0.1 ~ 0.5% of coarse biodiesel weight.
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Cited By (6)
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| CN104962397A (en) * | 2015-03-20 | 2015-10-07 | 南京工业大学 | Method for producing biodiesel through ester interchange in continuous-flow micro-channel reactor |
| CN107253913A (en) * | 2017-06-02 | 2017-10-17 | 中山致安化工科技有限公司 | Method for preparing chloroenyne by using microchannel reactor |
| CN110283071A (en) * | 2019-06-26 | 2019-09-27 | 南京理工大学 | A kind of system and method based on micro passage reaction synthesis of oxalic acid methyl ethyl ester |
| CN111375339A (en) * | 2018-12-30 | 2020-07-07 | 南通醋酸化工股份有限公司 | Batching device and solvent micro-mixing method in continuous preparation of acesulfame potassium |
| US11254883B2 (en) | 2020-06-30 | 2022-02-22 | Duke Technologies, Llc | Method and system for treating renewable feedstocks |
| US11525096B2 (en) | 2020-06-30 | 2022-12-13 | Duke Technologies, Llc | Method for treating renewable feedstocks |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962397A (en) * | 2015-03-20 | 2015-10-07 | 南京工业大学 | Method for producing biodiesel through ester interchange in continuous-flow micro-channel reactor |
| CN107253913A (en) * | 2017-06-02 | 2017-10-17 | 中山致安化工科技有限公司 | Method for preparing chloroenyne by using microchannel reactor |
| CN107253913B (en) * | 2017-06-02 | 2020-05-26 | 中山致安化工科技有限公司 | Method for preparing chloroenyne by using microchannel reactor |
| CN111375339A (en) * | 2018-12-30 | 2020-07-07 | 南通醋酸化工股份有限公司 | Batching device and solvent micro-mixing method in continuous preparation of acesulfame potassium |
| CN110283071A (en) * | 2019-06-26 | 2019-09-27 | 南京理工大学 | A kind of system and method based on micro passage reaction synthesis of oxalic acid methyl ethyl ester |
| US11254883B2 (en) | 2020-06-30 | 2022-02-22 | Duke Technologies, Llc | Method and system for treating renewable feedstocks |
| US11414609B2 (en) | 2020-06-30 | 2022-08-16 | Duke Technologies, Llc | System for treating renewable feedstocks |
| US11525096B2 (en) | 2020-06-30 | 2022-12-13 | Duke Technologies, Llc | Method for treating renewable feedstocks |
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