CN101280209B - Method for continuous production of biodiesel - Google Patents
Method for continuous production of biodiesel Download PDFInfo
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- CN101280209B CN101280209B CN2007100108957A CN200710010895A CN101280209B CN 101280209 B CN101280209 B CN 101280209B CN 2007100108957 A CN2007100108957 A CN 2007100108957A CN 200710010895 A CN200710010895 A CN 200710010895A CN 101280209 B CN101280209 B CN 101280209B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention relates to a method of producing bio-diesel continuously; animal, vegetable oil and low alcohol raw materials are reacted in a reactor composed of two parts and transformed into fatty acids short chain ester; namely, the bio-diesel; the first part of the reactor is a full-backmixing reactor used for providing high-efficiency mass transfer space for the raw materials so that the oils and the alcohols are enabled to be contacted sufficiently for reaction; the phase separation tendency of the mixture after reaction is reduced obviously; the second part of the reactor is a tubular reactor used for providing sufficient reaction time and space so that the raw materials are enabled to be transformed sufficiently for the generation of target product. Because reaction product from the reactor only contains very small quantity of residual glyceride, the product can fulfill the content requirement of the low carbon ester (such as methyl ester) in the product standards after the excessive lower alcohol and glycerol are separated from the product; thereby, the process of methyl ester distillation can be avoided.
Description
Technical field
The present invention relates to a kind of field of renewable energy technology, specifically be a kind of be raw material continuous production method of bio-diesel oil with the animal-plant oil.
Background technology
Biofuel, be the recyclable fuel that a kind of character of being obtained from reproducible biomass resource is similar to diesel oil, its main component be long-chains such as Palmiticacid, stearic acid, oleic acid, linolic acid saturated/or the ester compound that forms with alcohols materials such as methyl alcohol or ethanol of unsaturated fatty acids.
Because biofuel derives from the renewable biomass resource, do not contain in the mineral diesel materials such as common sulphur, aromatic hydrocarbon, after burning, can not produce SO
XParticulate matter is less, can effectively reduce the pollution of vehicle exhaust to environment, use biofuel can effectively reduce the concentration of CO, TPM etc. in the tail gas, to the contribution of Greenhouse effect only be mineral diesel 25% or lower, so research of biofuel and use the concern that more and more is subjected to various countries in recent years.
Present industrial production method of bio-diesel oil mainly contains two kinds, a kind of is that animal-plant oil and low-carbon alcohol get by transesterify in the presence of catalyzer, another kind is to need not catalyzer, utilizes supercritical process directly to carry out transesterification reaction under High Temperature High Pressure and makes.And according to the catalyzer difference of using, production method has two kinds of chemical method and biological enzymes.Chemical method mainly adopts acid, alkali as catalyzer, when using alkali (organic bases or mineral alkali) as catalyzer very high triglyceride transformation efficiency is arranged, but waste lye is difficult to separate from reaction product; When using acid as catalyzer, need higher temperature of reaction, power consumption height and yield are low.The speed of response of biological enzyme is slow, and it is long to reach the molecular balance required time, and is simultaneously obvious as the lipase deactivation phenomenom of catalyzer, and it is big to recycle difficulty, causes production cost to raise.And no matter adopt which kind of catalyzer, all there is following shortcoming in aforesaid method: the ester that reaction the obtains content of middle purpose product methyl esters mutually is generally 50%～90%, do not reach product standard and require (requiring more than 96.5% usually), must carry purpose product methyl esters dense as means such as distillations by separating, this has caused high energy consumption, and production efficiency is lower.
Because the polarity of methyl alcohol is stronger, do not dissolve each other with grease, in commercial process, all use the above stirred-tank reactor of two-stage or two-stage to carry out transesterify or esterification traditionally, and the reaction mass dispersion efficiency is not high in the popular response device, seek out satisfied methyl esters yield, have only the residence time that prolongs reaction mass, therefore caused unnecessary power consumption.
In order to solve catalyst separating and alcohol, the problem of grease phase-splitting, Chinese patent CN1408701A discloses a kind of method and apparatus for preparing fatty acid ester, under the condition of supercritical state and catalyzer existence, use the reactor of this invention to prepare fatty acid ester, wherein reactor is returned in the reaction mixture recirculation that contains unreacted reactant and/or intermediate product, the preferred temperature of this method is 240 ℃～400 ℃, preferred temperature is 245 ℃～350 ℃, preferred reaction pressure is 0.5MPa～25MPa, preferred reaction pressure is 2MPa～22MPa, preferred especially 8MPa～20MPa, this method has increased the reaction interface area, has improved transformation efficiency.Chinese patent CN1626621A also discloses a kind of method of fatty acid ester and fuel of fatty acid esters of preparing, this fatty acid ester is in the presence of catalyst-free, grease and alcohol both one of be to prepare under the condition of supercritical state, this method preferable reaction temperature is no more than 400 ℃, and preferred reaction pressure is 0.4MPa～25.0MPa.There is not the problem of catalyst separating in this method, and product need not circulate, so energy consumption is low.But because above two kinds of methods are all carried out, can cause the cracking of animal and plant grease inevitably under High Temperature High Pressure, have problems such as cost of equipment height, complicated operation simultaneously.
In order to solve unsaturated fatty acids chain generation cracked phenomenon under the high temperature, Chinese patent CN1740273A discloses a kind of continuous preparation method of bio-diesel oil.Its method is that grease and low-carbon alcohol are preheated to 30～200 ℃ through a tubular reactor, after mixing through mixing tank, enters overcritical tubular reactor and makes biofuel.Though this method is by reducing the cracking problem that the pure and mild grease residence time has at high temperature partly solved the unsaturated fatty acids chain, but still have that temperature of reaction is high 280～350 ℃, the situation of the high 16～50MPa of reaction pressure; Embodiment shows that also pure and mild grease must be higher than 50 minutes in the total residence time of device if seek out qualified biofuel product (fatty acid methyl ester is greater than 96.5%).
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of continuous production method of bio-diesel oil of suitability for industrialized.
Continuous production method of bio-diesel oil of the present invention comprises following content:
Animal and plant grease and low-carbon alcohol raw material be thorough mixing in full back-mixed reactors at first, carry out partial reaction, enter tubular reactor then, the abundant and low-carbon alcohol reaction generation ester fat acid low carbon alcohol ester of animal and plant grease in tubular reactor, reaction product is separated.Described full back-mixed reactors is a continuous stirred tank reactor (CSTR), or impact flow reactor, the preferred latter.
Reaction process of the present invention can be carried out under the catalyzer existence condition, also can not use catalyzer.When using catalyzer, can select the catalyzer of this area routine, as inorganic or organic acid, alkali, the organic alkali catalyst that the preferred reaction performance is high.When using catalyzer to deposit, the residence time of reaction mass in full back-mixed reactors is 0.1～1 hour, and temperature of reaction is 40 ℃～240 ℃, and reaction pressure is that normal pressure is extremely a little more than the vapour pressure of used lower alcohol raw material under temperature of reaction.Wherein preferable reaction temperature is 60 ℃～130 ℃, and preferred reaction pressure is the vapour pressure a little more than low-carbon alcohol, and the reaction times is relevant with catalyst system therefor.The residence time of reaction mass in tubular reactor is 0.1～3 hour, temperature of reaction is 40 ℃～240 ℃, reaction pressure is that normal pressure is extremely a little more than the vapour pressure of used lower alcohol raw material under temperature of reaction, wherein preferable reaction temperature is 60 ℃～170 ℃, and reaction pressure is relevant with catalyst system therefor with the reaction times.The reaction conditions of described tubular reactor can be identical with the reaction conditions of full back-mixed reactors, also can be the temperature that the temperature of reaction of tubular reactor is higher than full back-mixed reactors, make between the entrance and exit of tubular reactor and form a temperature gradient distribution from low to high.
Process of the present invention can be carried out not using under the catalyzer situation.The residence time of reaction mass in full back-mixed reactors is 0.1～1 hour, and temperature of reaction is 240 ℃～350 ℃, and reaction pressure is 10～30MPa; The residence time of reaction mass in tubular reactor is 0.1～1 hour, and temperature of reaction is 160 ℃～350 ℃, and reaction pressure is normal pressure～30MPa.The reaction conditions of described tubular reactor can be identical with the reaction conditions of full back-mixed reactors, also can be the temperature that the temperature of reaction of tubular reactor is lower than full back-mixed reactors, make between the entrance and exit of tubular reactor and form a temperature gradient distribution from high to low.
Described low-carbon alcohol is methyl alcohol or ethanol.
Described grease is animal tallow or Vegetable oil lipoprotein, as: one or more mixtures in suet, soybean oil, rapeseed oil, Oleum Gossypii semen, plam oil, sunflower seed oil, Rice pollard oil, genetically engineered soybean oil, Oleum Verniciae fordii, the Cortex jatrophae oil.
The mol ratio of described low-carbon alcohol and animal and plant grease is 5: 1～60: 1, preferred 6: 1～30: 1; Its adding mode can be once to add, and also can be to add in batches.
Described full back-mixed reactors adopts the full back-mixed reactors of the inner member that has the mutual disseminations of increase material such as rotating disk, it can be continuous stirred tank reactor (CSTR), also can be impact flow reactor, tank reactor and impact flow reactor can be determined by the design of this area general knowledge according to the reaction process conditional request.Preferred impact flow reactor.
Described tubular reactor can be coil pipe type reactor, arrange vertical pipe type or many horizontal rows tubular reactor more that the turbulent of increasing inner member can be arranged in the preferred tubular reactor, also can be the sky cartridge type.
Animal and plant grease and low-carbon alcohol are carried out in the ester-exchange reaction, the polarity of raw material low-carbon alcohol is strong, very poor with the grease intermiscibility, transesterification reaction is carried out at the interface at both, therefore need be with two kinds of raw material thorough mixing, and in reaction process, keeping this thorough mixing state, prior art and reaction unit are also all from improving two kinds of raw material dispersive angle design technological processs and structure of reactor.The present application people carries out the character of the reaction mechanism and the intermediateness material of ester-exchange reaction by research grease and low-carbon alcohol, find that transesterification reaction mainly is a proceed step by step, during the reaction beginning, the grease major part need be by the external force that continues to keep the thorough mixing of two kinds of materials between grease and the low-carbon alcohol based on Witepsol W-S 55.Along with the carrying out of reaction, Witepsol W-S 55 content reduces, and direactive glyceride content increases, and the material system mutual solubility after direactive glyceride and the dispersion of low-carbon alcohol thorough mixing strengthens, and the phase-splitting tendency of reaction mixture significantly reduces.Utilize the These characteristics of stearic exchange procedure, process engineering of the present invention is a two-stage reaction, the good full back-mixed reactors of dispersing property is adopted in first section reaction, in reaction process, keep the abundant contact of two kinds of raw materials to mix, realize oil, fat transforms to direactive glyceride from Witepsol W-S 55, reach when suiting transformation efficiency, the mutual solubility of reaction system strengthens, the tubular reactor that can enter plug flow further reacts, in tubular reactor, reaction mass still keeps the good mixing state, guarantees the abundant contact of two kinds of reaction raw materials, and then reaches the ideal reaction efficiency.In ester-exchange reaction, full back-mixed reactors can be material provides mass transfer space efficiently, makes grease fully disperse mutually to contact and react with alcohol mutually.The advantage of piston flow reactor is to continue to reduce the concentration of grease in reaction system, can reach the purpose that transforms substantially fully, its advantage is that the sepn process of product is simple, energy consumption is lower, tubular reactor can adopt the reaction process of gradient increased temperature and gradient cooling respectively according to the technology difference in reaction process in addition, by conditions such as adjustment temperature of reaction, the optimization synthesis reaction effect
Specifically, the present invention has following beneficial effect:
(1) reaction process both can be carried out having under the catalyzer low temperature situation, also can carry out under the overcritical situation of catalyst-free, and technological process is flexible, can adapt to the requirement of various glyceride stocks;
(2) adopt the reactor of two kinds of complete different types, solved the low problem of production technique mass-transfer efficiency in the past, can high-level efficiency, the production biofuel of continous-stable, suitability for industrialized production;
(3), all can produce standard compliant qualified biofuel product, and output is big, product with stable quality no matter adopt which kind of processing condition;
(4) adopt impact flow reactor as first section reactor of transesterify, greatly strengthen microcosmic and mixed and the microcosmic mass transfer, under the demulcent reaction conditions, reached high transformation efficiency, and form very even, the metastable reaction mass of mixing, help further reaction;
(5) owing to the only residual glyceryl ester that minute quantity is arranged from the reaction product that reaction unit comes out, material can satisfy in the product standard content requirement about low-carbon-ester (as methyl esters) after telling excessive lower alcohol and glycerine, thereby can save the process of distillation methyl esters, minimizing equipment reduces process cost.
(6) adopt the gradient increased temperature reaction process, exist down the material of full back-mixed reactors and the requirement of equipment to be reduced in catalyzer by the temperature of reaction that reduces full back-mixed reactors, and the temperature of reaction of passing through to improve tubular reactor has increased the speed that mono-glycerides transforms to the purpose product when prolonging the residence time.
(7) adopt the gradient cooling reaction process, reduced the residence time of reaction mass, reduced unsaturated fatty acids generation cracked phenomenon under the high temperature in the high-temperature zone; Avoid the use of fast cooling device simultaneously, greatly reduced process cost and facility investment.
Embodiment
The present invention proposes a kind of continuous production method of bio-diesel oil of suitability for industrialized.Animal and plant grease and low-carbon alcohol raw material fully react in dimeric reaction unit and change into ester fat acid low carbon alcohol ester, under the demulcent reaction conditions, it is poor with animal and plant grease mutual solubility to have solved alcohol, reaction system is two-phase, transesterification reaction is only carried out the problem that speed of reaction is low at the interface.Having simplified technical process, reduced production cost and facility investment, do not had discharging of waste liquid in the production process, is an environmental protection processing method.The production process of biofuel of the present invention comprises following content:
Animal and plant grease and low-carbon alcohol raw material fully react in dimeric reaction unit and change into ester fat acid low carbon alcohol ester.The first part of reaction unit is full back-mixed reactors such as impact flow reactor, can be material mass transfer space efficiently is provided, make grease fully disperse mutually to contact and react with alcohol mutually, carrying out along with reaction, Witepsol W-S 55 content reduces in the reaction system, direactive glyceride content increases, and the phase-splitting tendency of reaction back mixture significantly reduces; The second section of reaction unit is a tubular reactor, can be reaction mass the enough reaction times is provided, and makes reaction mass continue fully to transform and generate the purpose product; After telling excessive lower alcohol and glycerine, go aftertreatment or directly go out device from the reaction product that reaction unit comes out.
Further specify method of the present invention and effect below by embodiment.The percentage composition that relates to is the quality percentage composition.
Embodiment 1
Tubular reactor is heated to 200 ℃, 310 ℃ of the temperature of control impact flow reactor, pressure 18MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 40: 1, is that the speed of 6 times (being that residence time of material is 10 minutes) of impact flow reactor volume enters impact flow reactor with Oleum Gossypii semen and methyl alcohol with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 10 minutes, along with reaction mass in tubular reactor further reaction and flow, reaction mass forms one by 310 ℃ of thermogrades that progressively are reduced to 200 ℃ between the entrance and exit of tubular reactor, the mixture that is come out by tubular reactor steams except that most of residue methyl alcohol through flash distillation, the back cooling, standing separation, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 97.3%.
Embodiment 2
Tubular reactor is heated to 320 ℃, 320 ℃ of the temperature of control impact flow reactor, pressure 20MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 30: 1, is that the speed of 4 times (being that residence time of material is 15 minutes) of impact flow reactor volume enters impact flow reactor with Oleum Gossypii semen and methyl alcohol with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 30 minutes, the mixture that is come out by tubular reactor steams except that most of residue methyl alcohol through flash distillation, the back cooling, standing separation, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 94.1%.
Embodiment 3
Tubular reactor is heated to 160 ℃, 350 ℃ of the temperature of control impact flow reactor, pressure 25MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 50: 1, is that the speed of 8 times (being that residence time of material is 7.5 minutes) of impact flow reactor volume enters impact flow reactor with Oleum Gossypii semen and methyl alcohol with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 15 minutes, along with reaction mass in tubular reactor further reaction and flow, reaction mass forms one by 350 ℃ of thermogrades that progressively are reduced to 160 ℃ between the entrance and exit of tubular reactor, the mixture that is come out by tubular reactor steams except that most of residue methyl alcohol through flash distillation, the back cooling, standing separation, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 95.5%.
Embodiment 4
The employing triethylamine is a catalyzer, add-on is 3% of an oil quality, tubular reactor is heated to 170 ℃, 120 ℃ of the temperature of control impact flow reactor, pressure 1.0MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 10: 1, Oleum Gossypii semen and methyl alcohol are that the speed of 2 times (being that residence time of material is 30 minutes) of impact flow reactor volume enters impact flow reactor with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 30 minutes, along with reaction mass in tubular reactor further reaction and flow, reaction mass forms one by 120 ℃ of thermogrades that progressively are elevated to 170 ℃ between the entrance and exit of tubular reactor, the mixture that is come out by tubular reactor steams except that most of residue methyl alcohol through flash distillation, the back cooling, standing separation, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 98.2%.
Embodiment 5
The employing diethylamine is a catalyzer, add-on is 2% of an oil quality, tubular reactor is heated to 130 ℃, 130 ℃ of the temperature of control impact flow reactor, pressure 1.0MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 8: 1, Oleum Gossypii semen and methyl alcohol are that the speed of 2.5 times (being that residence time of material is 24 minutes) of impact flow reactor volume enters impact flow reactor with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 20 minutes, and the mixture that is come out by tubular reactor steams except that most of residue methyl alcohol, back cooling through flash distillation, standing separation, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 93.8%.
Embodiment 6
The employing Diisopropylamine is a catalyzer, add-on is 5% of an oil quality, tubular reactor is heated to 240 ℃, 90 ℃ of the temperature of control impact flow reactor, pressure 0.7MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 12: 1, Oleum Gossypii semen and methyl alcohol are that the speed of 1 times (being that residence time of material is 60 minutes) of impact flow reactor volume enters impact flow reactor with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 80 minutes, along with reaction mass in tubular reactor further reaction and flow, reaction mass forms one by 90 ℃ of thermogrades that progressively are elevated to 240 ℃ between the entrance and exit of tubular reactor, the mixture that is come out by tubular reactor steams except that most of residue methyl alcohol through flash distillation, the back cooling, standing separation, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 93.4%.
Embodiment 7
The employing diethylamine is a catalyzer, add-on is 4% of an oil quality, tubular reactor is heated to 120 ℃, 120 ℃ of the temperature of control impact flow reactor, pressure 2.5MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 15: 1, Oleum Gossypii semen and methyl alcohol are that the speed of 2 times (being that residence time of material is 30 minutes) of impact flow reactor volume enters impact flow reactor with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 120 minutes, and the mixture that is come out by tubular reactor steams except that most of residue methyl alcohol, back cooling through flash distillation, standing separation, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 98.7%.
Embodiment 8
The employing diethylamine is a catalyzer, add-on is 6% of an oil quality, tubular reactor is heated to 240 ℃, 240 ℃ of the temperature of control impact flow reactor, pressure 10MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 8: 1, Oleum Gossypii semen and methyl alcohol are that the speed of 4 times (being that residence time of material is 15 minutes) of impact flow reactor volume enters impact flow reactor with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 30 minutes, and the mixture that is come out by tubular reactor steams except that most of residue methyl alcohol, back cooling through flash distillation, standing separation, obtain fatty acid ester phase (upper strata), utilize the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 97.1%.
Embodiment 9
Employing potassium hydroxide is catalyzer, add-on is 1% of an oil quality, tubular reactor is heated to 50 ℃, 90 ℃ of the temperature of control impact flow reactor, pressure 0.7MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 10: 1, Oleum Gossypii semen and methyl alcohol are that the speed of 4 times (being that residence time of material is 15 minutes) of impact flow reactor volume enters impact flow reactor with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 30 minutes, along with reaction mass in tubular reactor further reaction and flow, reaction mass forms one by 90 ℃ of thermogrades that progressively are reduced to 50 ℃ between the entrance and exit of tubular reactor, lower the temperature by the mixture process that tubular reactor comes out, standing separation obtains fatty acid ester phase (upper strata), utilizes the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 95.8%.
Embodiment 10
Employing potassium hydroxide is catalyzer, add-on is 2% of an oil quality, tubular reactor is heated to 80 ℃, 100 ℃ of the temperature of control impact flow reactor, pressure 0.9MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 5: 1, Oleum Gossypii semen and methyl alcohol are that the speed of 3 times (being that residence time of material is 20 minutes) of impact flow reactor volume enters impact flow reactor with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 30 minutes, along with reaction mass in tubular reactor further reaction and flow, reaction mass forms one by 100 ℃ of thermogrades that progressively are reduced to 80 ℃ between the entrance and exit of tubular reactor, lower the temperature by the mixture process that tubular reactor comes out, standing separation obtains fatty acid ester phase (upper strata), utilizes the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 94.9%.
Embodiment 11
Employing potassium hydroxide is catalyzer, add-on is 1% of an oil quality, tubular reactor is heated to 40 ℃, 60 ℃ of the temperature of control impact flow reactor, pressure 0.3MPa, the mol ratio of methyl alcohol and Oleum Gossypii semen is 8: 1, Oleum Gossypii semen and methyl alcohol are that the speed of 2 times (being that residence time of material is 30 minutes) of impact flow reactor volume enters impact flow reactor with the feed volume flow, grease and methyl alcohol are fully disperseed, after the reaction, enter tubular reactor, in the residence time of tubular reactor is 10 minutes, along with reaction mass in tubular reactor further reaction and flow, reaction mass forms one by 60 ℃ of thermogrades that progressively are reduced to 40 ℃ between the entrance and exit of tubular reactor, lower the temperature by the mixture process that tubular reactor comes out, standing separation obtains fatty acid ester phase (upper strata), utilizes the 6890N gas chromatograph analysis of Agilent company, recording the fatty acid triglycercide transformation efficiency is 100%, and the fatty acid ester content of middle methyl esters mutually is 96.5%.
Claims (12)
1. continuous production method of bio-diesel oil, comprise following content: animal and plant grease and low-carbon alcohol raw material be thorough mixing in full back-mixed reactors at first, carry out partial reaction, enter tubular reactor then, abundant and the low-carbon alcohol reaction generation fatty acid ester of low-carbon alcohol of animal and plant grease in tubular reactor, reaction product is separated.
2. in accordance with the method for claim 1, it is characterized in that described full back-mixed reactors is a continuous stirred tank reactor (CSTR), or impact flow reactor.
3. in accordance with the method for claim 1, it is characterized in that described reaction process carries out under the catalyzer existence condition, the residence time of reaction mass in full back-mixed reactors is 0.1～1 hour, temperature of reaction is 40 ℃～240 ℃, and reaction pressure is that normal pressure is extremely a little more than the vapour pressure of used lower alcohol raw material under temperature of reaction; The residence time of reaction mass in tubular reactor is 0.1～3 hour, and temperature of reaction is 40 ℃～240 ℃, and reaction pressure is that normal pressure is extremely a little more than the vapour pressure of used lower alcohol raw material under temperature of reaction.
4. in accordance with the method for claim 1, it is characterized in that described reaction do not use catalyzer, the residence time of reaction mass in full back-mixed reactors is 0.1～1 hour, and temperature of reaction is 240 ℃～350 ℃, and reaction pressure is 10～30MPa; The residence time of reaction mass in tubular reactor is 0.1～1 hour, and temperature of reaction is 160 ℃～350 ℃, and reaction pressure is normal pressure～30MPa.
5. in accordance with the method for claim 1, it is characterized in that described low-carbon alcohol is methyl alcohol or ethanol.
6. according to claim 1 or 5 described methods, it is characterized in that described low-carbon alcohol can be once to add, also can be to add with certain proportion in batches.
7. in accordance with the method for claim 1, it is characterized in that described animal and plant grease is one or more mixtures in suet, soybean oil, rapeseed oil, Oleum Gossypii semen, plam oil, sunflower seed oil, Rice pollard oil, genetically engineered soybean oil, Oleum Verniciae fordii, the Cortex jatrophae oil.
8. according to claim 1 or 5 or 6 or 7 described methods, the mol ratio that it is characterized in that described low-carbon alcohol and animal and plant grease is 5: 1～60: 1.
9. in accordance with the method for claim 1, it is characterized in that described tubular reactor is coil pipe type reactor, arranges vertical pipe type or many horizontal rows tubular reactor more.
10. in accordance with the method for claim 3, it is characterized in that described catalyzer is inorganic or organic acid, alkali.
11. according to claim 1,3 or 9 described methods, the reaction conditions that it is characterized in that described tubular reactor is identical with the reaction conditions of full back-mixed reactors, or the temperature of reaction of tubular reactor is higher than the temperature of full back-mixed reactors, makes between the entrance and exit of tubular reactor and forms a temperature gradient distribution from low to high.
12. according to claim 1,4 or 9 described methods, the reaction conditions that it is characterized in that described tubular reactor is identical with the reaction conditions of full back-mixed reactors, or the temperature of reaction of tubular reactor is lower than the temperature of full back-mixed reactors, makes between the entrance and exit of tubular reactor and forms a temperature gradient distribution from high to low.
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| CN102250695A (en) * | 2011-06-23 | 2011-11-23 | 南昌大学 | Method for continuously converting oil into fatty acid short chain alcohol ester |
| CN104403805B (en) * | 2014-09-29 | 2017-02-15 | 成都新柯力化工科技有限公司 | Biodiesel preparation method |
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| CN1408701A (en) * | 2001-09-28 | 2003-04-09 | 住友化学工业株式会社 | Method and device for preparing fatty acid ester |
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| CN1408701A (en) * | 2001-09-28 | 2003-04-09 | 住友化学工业株式会社 | Method and device for preparing fatty acid ester |
| CN1626621A (en) * | 2003-12-11 | 2005-06-15 | 北京化工大学 | New method for producing biology diesel oil from vegetable oil |
| CN1740273A (en) * | 2005-09-09 | 2006-03-01 | 清华大学 | Continuous biological diesel oil preparing process |
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