CN100360644C - Production process of biological diesel - Google Patents
Production process of biological diesel Download PDFInfo
- Publication number
- CN100360644C CN100360644C CNB2005100464276A CN200510046427A CN100360644C CN 100360644 C CN100360644 C CN 100360644C CN B2005100464276 A CNB2005100464276 A CN B2005100464276A CN 200510046427 A CN200510046427 A CN 200510046427A CN 100360644 C CN100360644 C CN 100360644C
- Authority
- CN
- China
- Prior art keywords
- oil
- accordance
- reaction
- fatty acid
- fat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Fats And Perfumes (AREA)
Abstract
The present invention relates to a method for producing biological diesel fuel from fat acid triglyceride, particularly to fat and oil of animals and plants. The method of the present invention uses solid base as a catalyst and is added with a certain amount of amine substance to form a third component. High conversion rate can be obtained under moderated conditions, and the service life of the catalyst is long. Compared with the prior art, the method of the present invention has the advantages of simple process, moderated condition, high conversion rate, less side product, long catalyst life, etc., and can producing the biological diesel fuel by using the fat and the oil of various animals and plants.
Description
Technical field
The present invention relates to a kind of production method of biofuel, particularly from fatty acid triglyceride, especially driven, vegetable tallow and oil, production method of bio-diesel oil.
Background technology
Fatty acid triglyceride, particularly animal and plant fat and oil carry out the monoester that transesterification reaction obtains with the lower molecular weight monohydroxy-alcohol, to the diesel oil that obtains from petroleum fractions similar character are arranged, can be used as fuel and use, generally the fuel that will obtain in this way is called biofuel.
The biofuel of producing by greasy transesterification reaction has the following advantages: 1) good environmental protection characteristic is arranged.The biofuel sulphur content is low, does not contain the aromatic hydrocarbon that environment is polluted.2) engine cold-starting performance is preferably arranged, additive-free condensation point reaches-20 ℃.3) lubricity is preferably arranged, can reduce the wear rate of oil injection pump, engine cylinder-body and connecting rod, prolong its work-ing life.4) good safety performance is arranged, its flash-point height does not belong to hazardous substance.5) good fuel performance is arranged, its cetane value height, combustionproperty is better than ordinary diesel oil.6) has recyclability.Biofuel is as a kind of renewable energy source, and its resource can be inexhausted.
At present, mainly adopt chemical ester-interchange method production biofuel, use acid, alkali and molecular sieve as catalyzer.When using alkali (organic bases or mineral alkali), when alkali concn is too high, can cause side reaction to take place as catalyzer.Alkali and product carry out saponification reaction, cause productive rate to descend.When using acid as catalyzer, need higher temperature, the acid-catalyzed transesterification reaction is a reversible.Power consumption height and yield are low.When using molecular sieve as catalyzer, need carry out transesterification reaction under higher temperature of reaction, this moment, methyl alcohol was vapor state, was unfavorable for the carrying out that reacts.No matter adopt the sort of catalyzer, all there is following shortcoming in aforesaid method: complex process, alcohol must be excessive, and subsequent technique must have corresponding pure retrieving arrangement, energy consumption height; Product color is dark, because unsaturated fatty acids is at high temperature apt to deteriorate in the fat; Esterification products is difficult to reclaim the cost height; Discharging of waste liquid is arranged in the production process.In addition, in the prior art ester that obtains of reaction mutually in, purpose product (as methyl esters) content lower (being generally 50%～70%), must a large amount of monoglycerides and triglyceride be looped back reactor by separating, in fact cause the reactor utilization ratio to reduce, the raw material processing power descends, and production efficiency is lower.
In order to solve the problem of discharging of waste liquid in the production process, people bring into use the biological enzyme biodiesel synthesis, and this method has mild condition, and pure consumption is little, advantages such as non-pollution discharge.Shortcoming is: greasy transformation efficiency is low; The work-ing life of enzyme is short; Product is difficult to separate with glycerine; Lipase price height; Therefore there is not industrial application value.
In order to solve the problem of catalyst separating, 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, 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 ℃, and preferred temperature is 245 ℃～350 ℃, and preferred reaction pressure is 0.5MPa～25MPa, and preferred reaction pressure is 2MPa～22MPa, preferred especially 8MPa～20MPa.This method has increased the reaction interface area, has improved transformation efficiency.Chinese patent CN1408701A 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 under the condition of supercritical state, grease and pure prepared in reaction.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 being carried out, can cause the cracking of animal and plant grease under High Temperature High Pressure, have the high problem of cost of equipment simultaneously.
In order to improve the rate of recovery of product, Chinese patent CN1230945A discloses a kind of from fatty acid triglyceride, especially animal or plant fat and oil, in the presence of homogeneous phase or different-phase catalyst with the method for a kind of lower molecular weight monohydroxy-alcohol by transesterification production fatty acid ester.The fatty acid ester that generates according to this method is extracted from reaction mixture by a kind of extraction agent, and the fatty acid ester purity that obtains like this is higher.The most handy a kind of to have reduced temperature 20 ℃ the time about 0.7 as extraction agent, preferably is equal to or greater than 0.7 low-pressure gas.Preferred extraction agent is carbonic acid gas, propane, butane, dme, ethyl acetate or their mixture.This method makes technological process become complicated in order to improve the yield of product, and still has catalyst separating, the problem that the grease transformation efficiency is low.
Because alcohol is poor with animal and plant grease mutual solubility; reaction system is two-phase, and transesterification reaction is only carried out at the interface, and speed of reaction is low; in order to improve transformation efficiency, Chinese patent CN1496398A discloses a kind of method that obtains fatty acid ester by alcoholysis from the triacylglycerol ester.In order to accelerate ester-exchange reaction, add a certain amount of at least a alkanol fatty acid ester in initial reaction phase, especially monobasic chain triacontanol ester, preferred methyl esters, ethyl ester and/or ethyl ester, in fat that pending transesterify is arranged and/or oil, so that the reaction mixture that generates thus is made of single-phase.Thereby make this process just keep high reaction rate from beginning.And solved the problem of lipid acid to the reaction conversion ratio influence.Because the starting stage of transesterify can be avoided or shorten to this method, shortened the reaction times, but the selectivity and the transformation efficiency of transesterification reaction there is not too big contribution; Reaction needed is carried out cyclical operation, has increased energy consumption; The selected catalyzer price of reaction process height; Ester-exchange reaction itself generates water, and water is poisonous to reacting selected catalyzer, so catalyst life is short; The catalytic activity salt that is insoluble to reaction mixture will be deposited on the carrier, and catalyzer is made and/or the sepn process complexity.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of novel method of production biofuel.The inventive method has reached high transformation efficiency under the demulcent reaction conditions.Avoid catalyst separating, simplified technical process, reduced production cost and facility investment.Not having 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: with animal and vegetable oil or fat that contains fatty acid triglycercide and the monohydroxy-alcohol with 1～8 carbon atom is raw material, with the solid alkali is heterogeneous catalyst, in reaction raw materials, add simultaneously a certain amount of amine substance, in production biofuel under the demulcent reaction conditions and under the higher transformation efficiency.
Amine substance is the organic amine that contains 1～6 carbon atom, and add-on is 0.1%～50% of raw material fat or a weight of oil, and is preferred 1%～30%, most preferably 5%～20%.
Solid base catalyst can be one or more in the molecular sieve of anionite-exchange resin, metal oxide, metallic salt, mixed oxide and various basic metal and alkaline-earth metal exchange, preferred anionic exchange resin, particularly strong basic type anion-exchange resin.
Transesterification reaction is 30 ℃～150 ℃ of temperature ranges, and preferred 30 ℃～100 ℃, what override was selected is to carry out between 40 ℃～65 ℃.Reaction is to carry out to the pressure of the vapour pressure of lower molecular weight monohydroxy-alcohol at normal pressure.
Any fatty acid glyceryl ester can be made raw material of the present invention, and especially preferred is to have 10～22 carbon atoms with in animal and plant fat and/or the oil, particularly those fatty acid radicals, and preferably 12～18 carbon atoms makes raw material.As the example of vegetable raw material can enumerate soybean oil, rapeseed oil, sunflower seed oil, peanut oil, Oleum Gossypii semen, plam oil, Semen Lini oil, Viscotrol C, beet oil and olive wet goods one or more.The example of animal raw materials such as butter, lard one or both.
The present invention uses lower molecular weight monohydroxy-alcohol and fatty acid glyceryl ester with 1～8 carbon atom to carry out transesterification reaction.The alcohol that preferably has 1～6 carbon atom, special particular methanol or ethanol.
Be applicable to that amine substance of the present invention comprises: the mixture of one or more of methylamine, dimethylamine, Trimethylamine 99, third rare amine, the rare amine of dipropyl, 3 third rare amine, Isopropylamine, Diisopropylamine, ethamine, diethylamine, triethylamine, 2-DEHA, propylamine, n-Butyl Amine 99, t-butylamine, sec-butylamine, monoethanolamine.What preferentially select is a kind of or mixture of ethamine, diethylamine, Diisopropylamine, as the 3rd component.
According to the invention process method, the heterogeneous catalyst that is adopted is a solid alkali, comprising: the molecular sieve of anionite-exchange resin, metal oxide, metallic salt, mixed oxide and various basic metal and alkaline-earth metal exchange, the preferred anionic exchange resin, especially the strongly basic anion exchange resin optimum is as catalyzer of the present invention.When using strongly basic anion exchange resin, to be transformed into the hydrogen-oxygen type from the chlorine type before using as catalyzer.Make the transition hydrochloric acid soln and the 1N sodium hydroxide solution of available 1N, ion-exchange is finished, and then uses anhydrous methyl alcohol drying, just can obtain a kind of strongly basic anion exchange resin based on synthetic resins (polystyrene/divinylbenzene).Promptly can be used as catalyzer of the present invention.
Continous way operation or batch operation are adopted in reaction, and continous way operation hourly space velocity is generally 0.5～5h
-1, the batch operation the reaction time is generally 0.5～5h.
When adopting the fixed bed operate continuously, strongly basic anion exchange resin after at first will making the transition is packed in the fixed-bed reactor, then with reaction raw materials fatty acid glyceryl ester, lower molecular weight monohydroxy-alcohol and the 3rd component, under required temperature of reaction, successive feeds in the fixed-bed reactor, and reaction product is discharged continuously, and the product of discharge is through distillation procedure, unreacted alcohols material and the 3rd component can be separated, recycle then.Through the reaction product after the distillation, standing separation, the upper strata ester promptly can be used as the biofuel product mutually and uses, and lower floor is that the glycerine of purity more than 80% can be used as the byproduct sale.Sometimes the reaction product of discharging continuously is without above-mentioned distillation procedure, and direct standing separation can obtain biofuel product and purity and be the glycerine more than 80%.
When adopting the periodical operation of still formula, reaction raw materials fatty acid glyceryl ester, lower molecular weight monohydroxy-alcohol, the 3rd component and catalyzer are put into reactor in the lump, stir then and be warmed up to required temperature of reaction simultaneously, react.Reaction is emitted reaction product after finishing, and carries out distillation procedure, unreacted alcohols material and the 3rd component can be separated, and recirculation is used.Standing separation then, the upper strata that obtains promptly is the biofuel product.Lower floor is that to contain purity be glycerine phase more than 80%.The reaction product of emitting sometimes is without above-mentioned distillation procedure, and direct standing separation can obtain biofuel product and purity and be the glycerine more than 80%.
According to the present invention, transesterification reaction is to carry out under the pressure between the vapour pressure of selected alcohol at normal pressure.Generally arrive 2.0MPa, preferred 0.10MPa～1.00MPa at normal pressure.Suitable pressure can increase the reaction interface area, improves greasy transformation efficiency.
According to implementation method of the present invention, the mol ratio that transesterification reaction is chosen lower molecular weight monohydroxy-alcohol and animal and plant fat and oil is 3～50, and is preferred 5～30, and what override was selected is 5～15.But find that by test when the add-on of monohydroxy-alcohol was slightly larger than theoretical amount, the selectivity of reaction and transformation efficiency all had raising.
According to implementation method of the present invention, when adopting batch operation, be benchmark with animal and plant fat and oil, the add-on of heterogeneous catalyst is about 1%～30%, and is preferred 5%～20%, and what override was selected is 5%～10%.
Through discovering in a large number, raw material fat or the mutual solubility between oil and the lower alcohol used in the production of biodiesel process are relatively poor, and reaction only takes place at the two-phase interface place, causes speed of response lower, and transformation efficiency can't improve.The inventive method increases the mutual solubility of fatty acid triglyceride and lower molecular weight monohydroxy-alcohol by introducing the 3rd component, has improved mass-transfer efficiency, has accelerated speed of response, has improved greasy transformation efficiency, has reduced the reaction severity.In reaction process, the 3rd component cooperates with Primary Catalysts simultaneously, has obtained to prolong the catalyzer beyond thought effect in work-ing life.And when using the combination of strongly basic anion exchange resin and amine, beyond thought is that greasy transformation efficiency increases substantially, and has therefore reduced the treating process of product and by product, has simplified technical process, low production cost and facility investment.It should be noted that especially, the ester that the present invention obtains mutually in, purpose product (as methyl esters) content unexpectedly improves, generally can reach more than 94.5%, just the purpose product selectivity is high especially, need the amount of round-robin monoglyceride and triglyceride to significantly reduce, the result is that the reactor of identical scale can be handled more raw materials, and efficient improves greatly.In addition, the present invention adopts heterogeneous catalyst (solid base catalyst), has avoided the pollution to product of the separation of catalyzer and catalyzer.
Embodiment
Further specify method of the present invention and effect below by embodiment and comparative example.(percentage composition is benchmark with the weight percentage)
Embodiment 1
With strongly basic anion exchange resin (D201x7, Dandong No.3 Chemical Factory produces) 10 grams, methyl alcohol 70 grams and Oleum Gossypii semen 200 grams, diethylamine 20 grams join in the four-hole glass flask that has thermometer, stirring and condenser, start stirring and simultaneously the temperature of charge in the four-hole glass flask are heated to 65 ℃.Reacted 2 hours.After reaction finishes, under normal pressure, distill, till methyl alcohol and diethylamine no longer distillate, stop distillation, be cooled to room temperature, filter out standing separation behind the catalyzer, obtain fatty acid ester phase (upper strata), the GC-14B gas chromatograph analysis of Tianjin company is led in utilization, and recording the fatty acid triglycercide transformation efficiency is 95.6%, and the fatty acid ester content of middle methyl esters mutually is 96.8%.
Comparative example 1
With strongly basic anion exchange resin (D201x7, Dandong No.3 Chemical Factory produces) 150 grams, methyl alcohol 70 grams join in the autoclave with the 200g Oleum Gossypii semen, start stirring and simultaneously the temperature of charge in the autoclave are heated to 65 ℃.Reacted 2 hours.Reaction filters out catalyzer after finishing, and the gained reactant is analyzed, and utilizes the GC-14B gas chromatograph analysis of leading Tianjin company, and recording the fatty acid triglycercide transformation efficiency is 80%, and the fatty acid ester content of middle methyl esters mutually is 54%.
Embodiment 2
With strongly basic anion exchange resin (D201x7) 10 grams, join in the autoclave earlier, then methyl alcohol 70 gram and diethylamine 20 grams and Oleum Gossypii semen 200 are restrained mix after, be heated to 65 ℃, squeeze in the autoclave with pump, the reaction times is 0.5 hour, reaction finishes postcooling, use the GC-14B gas chromatograph analysis of leading Tianjin company after filtering out catalyzer, recording the fatty acid triglycercide transformation efficiency is 94.8%, and the fatty acid ester content of middle methyl esters mutually is 95.7%.
Comparative example 2
Method according to embodiment 2, with 25g particulate arginine zinc, join in the autoclave earlier, then with methyl alcohol 70 gram with contain lipid acid 11.2%, fatty mono glyceride 6.2%, fatty acid diglyceride 3.8%, after Oleum Gossypii semen 200 grams of fatty acid triglycercide 78.8% mix, be heated to 65 ℃, squeeze in the autoclave with pump, at 125 ℃, 0.5MPa under the pressure, reacted 20 minutes, reaction finishes postcooling, filters out behind the catalyzer with the GC-14B gas chromatograph analysis of leading Tianjin company, record and contain 86% fatty acid methyl ester in the reaction mixture, the fatty acid ester content of middle methyl esters mutually is 65.8%.
Comparative example 3
Press the method for embodiment 2, do not add the resin anion(R.A) catalyzer, other condition is identical with embodiment 2, and the fatty acid triglycercide transformation efficiency is 93.3%, and the fatty acid ester content of middle methyl esters mutually is 75.0%.
Embodiment 3
According to the method for embodiment 1, just changing temperature of reaction is 30 ℃, 50 ℃, and recording the fatty acid triglycercide transformation efficiency is 80.5%, 90.6%, and the fatty acid ester content of middle methyl esters mutually is respectively 94.3%, 95.7%.
Embodiment 4
Method according to embodiment 1, the molecular ratio that just changes methyl alcohol and Oleum Gossypii semen is 5,8,10,20 o'clock, recording the fatty acid triglycercide transformation efficiency is 92.7%, 93.5%, 94.4%, 96.0%, and the fatty acid ester content of middle methyl esters mutually is respectively 94.7%, 95.9%, 96.5%, 97.0%.
Embodiment 5
According to the method for embodiment 1, the add-on that just changes the 3rd component is 3%, 5%, 10%, 30% o'clock, and recording the fatty acid triglycercide transformation efficiency is 89.6%, 93.6%, 95.2%, 97.0%.The fatty acid ester content of middle methyl esters mutually is respectively 94.9%, 96.2%, 96.9%, 97.5%.
Embodiment 6
Method according to embodiment 1, change the 3rd component into Diisopropylamine, when temperature of reaction was respectively 30 ℃, 50 ℃, 60 ℃, recording the fatty acid triglycercide transformation efficiency was 75.5%, 90.6%, 92.4%, and the fatty acid ester content of middle methyl esters mutually is respectively 95.0%, 96.4%, 97.3%.
Embodiment 7
Method according to embodiment 1, also adopting Diisopropylamine is the 3rd component, the molecular ratio that changes methyl alcohol and Oleum Gossypii semen is 7,8,10,15 o'clock, recording the fatty acid triglycercide transformation efficiency is 89.7%, 90.6%, 91.3%, 93.7%, and the fatty acid ester content of middle methyl esters mutually is respectively 95.1%, 96.3%, 97.0%, 98.1%.
Embodiment 8
Method according to embodiment 1, the add-on that just changes Diisopropylamine is 1%, 10%, 20%, 25% o'clock, recording the fatty acid triglycercide transformation efficiency is 75.5%, 92.1%, 94.5%, 94.3%, and the fatty acid ester content of middle methyl esters mutually is respectively 94.8%, 95.7%, 96.5%, 98.1%.
Embodiment 9
According to the method for embodiment 2, change the 3rd component into ethamine, when temperature of reaction was respectively 50 ℃, recording the fatty acid triglycercide transformation efficiency was 92.6%, the fatty acid ester content of middle methyl esters mutually is 95.4%.
Embodiment 10
According to the method for embodiment 2, also adopting ethamine is the 3rd component, and the molecular ratio that changes methyl alcohol and Oleum Gossypii semen is 10 o'clock, and recording the fatty acid triglycercide transformation efficiency is 93.8%, and the fatty acid ester content of middle methyl esters mutually is 95.7%.
Embodiment 11
According to the method for embodiment 2, the add-on that just changes ethamine is 5%, 10%, 15% o'clock, and recording the fatty acid triglycercide transformation efficiency is 90.5%, 94.6%, 95.7%, and the fatty acid ester content of middle methyl esters mutually is respectively 94.5%, 95.7%, 97.4%.
Embodiment 12
Strongly basic anion exchange resin (with embodiment 1) 50g is packed in the fixed-bed reactor, then with methyl alcohol with (contain lipid acid 11.2%, fatty mono glyceride 6.2%, fatty acid diglyceride 3.8%, fatty acid triglycercide 78.8%) ratio of the branch of Oleum Gossypii semen is 10, and diethylamine is 10% to the weight of Oleum Gossypii semen, successive feeds in the fixed-bed reactor, under 60 ℃ of temperature of reaction, normal pressure, air speed 0.5h
-1Reaction product is discharged continuously, the product of discharging is through distillation procedure, isolate unreacted pure and mild the 3rd component, standing separation then, with the GC-14B gas chromatograph analysis of leading Tianjin company, record the fatty acid triglycercide transformation efficiency is 96.2% to the upper strata ester mutually, and the fatty acid ester content of middle methyl esters mutually is 96.1%.The liquid chromatograph analysis of lower floor's glycerine, purity 85.2%.
Embodiment 13
According to the method for embodiment 12, just changing diethylamine is Diisopropylamine, and recording the fatty acid triglycercide transformation efficiency is 90.6%, and the fatty acid ester content of middle methyl esters mutually is 95.0%.
Embodiment 14
According to the method for embodiment 12, just changing diethylamine is ethamine, and recording the fatty acid triglycercide transformation efficiency is 94.8%, and the fatty acid ester content of middle methyl esters mutually is 94.6%.
Embodiment 15
Press the method for embodiment 2, change methyl alcohol into ethanol, consumption is 10 with Oleum Gossypii semen molecule ratio, and temperature of reaction is 70 ℃, and other is identical with embodiment 2, and the fatty acid triglycercide transformation efficiency is 93%, and the fatty acid ester content of middle ethyl ester mutually is respectively 95.4%.
Embodiment 16
Press the method for embodiment 2, change Oleum Gossypii semen into sunflower seed oil, other is identical with embodiment 2, and the fatty acid triglycercide transformation efficiency is 95%, and the fatty acid ester content of middle methyl esters mutually is respectively 95.0%.
Embodiment 17
Press the method for embodiment 1, after catalyzer was reused 5 times, the fatty acid triglycercide transformation efficiency was 95.0%, and the fatty acid ester content of middle methyl esters mutually is 95.1%.After catalyzer was reused 10 times, the fatty acid triglycercide transformation efficiency was 94.8%, and the fatty acid ester content of middle methyl esters mutually is 94.8%, and the selectivity of catalyst activity and methyl esters does not have to change substantially.
Comparative example 4
Press the method for comparative example 1, after catalyzer was reused 5 times, the fatty acid triglycercide transformation efficiency was 75.5%, and the fatty acid ester content of middle methyl esters mutually is 55%.After catalyzer was reused 10 times, the fatty acid triglycercide transformation efficiency was 70.6%, and the fatty acid ester content of middle methyl esters mutually is 52%, and catalyst activity and purpose product selectivity all have tangible reduction.
Embodiment 18
According to the method for embodiment 2, with 8 gram magnesium aluminum oxides (Mg-Al composite oxide, magnalium atomic ratio are 3: 1), join earlier in the autoclave, then with methyl alcohol 104 gram, after diethylamine 20 grams and Oleum Gossypii semen 200 restrain and mix, join in the autoclave, under 130 ℃, 0.6MPa pressure, to react 3 hours, reaction finishes postcooling, filter out catalyzer, steam excessive methanol, recording the fatty acid triglycercide transformation efficiency is 96.6%, and the fatty acid ester content of middle methyl esters mutually is respectively 95.0%.
Embodiment 19
According to the method for embodiment 18, just change diethylamine into Diisopropylamine, recording the fatty acid triglycercide transformation efficiency is 95.4%, the fatty acid ester content of middle methyl esters mutually is respectively 95.6%.
Embodiment 20
According to the method for embodiment 18, after catalyzer was reused 5 times, the fatty acid triglycercide transformation efficiency was 96.4%, and the fatty acid ester content of middle methyl esters mutually is 95.1%.After catalyzer was reused 10 times, the fatty acid triglycercide transformation efficiency was 95.8%, and the fatty acid ester content of middle methyl esters mutually is 95.1%, and the selectivity of catalyst activity and methyl esters does not have to change substantially.
Claims (15)
1, a kind of production method of biofuel, process comprises: with the animal and vegetable oil or the fat of fatty acids triglyceride level, and the monohydroxy-alcohol with 1～8 carbon atom is a raw material, with the solid alkali is heterogeneous catalyst, in reaction raw materials, add simultaneously amine substance, production biofuel under the condition of 30 ℃～150 ℃ of temperature of reaction; Wherein amine substance is the organic amine that contains 1～6 carbon atom, and add-on is 0.1%～50% of raw material fat or a weight of oil.
2, in accordance with the method for claim 1, it is characterized in that described amine substance add-on is 1%～30%.
3, in accordance with the method for claim 1, it is characterized in that described amine substance add-on is 5%～20%.
4, in accordance with the method for claim 1, it is characterized in that described solid base catalyst is one or more in the molecular sieve of anionite-exchange resin, metal oxide, metallic salt, mixed oxide and various basic metal and alkaline-earth metal exchange.
5, in accordance with the method for claim 1, it is characterized in that described solid base catalyst is a strong basic type anion-exchange resin.
6, in accordance with the method for claim 1, it is characterized in that described being reflected under 30 ℃～100 ℃ carry out.
7, in accordance with the method for claim 1, it is characterized in that described being reflected under 40 ℃～65 ℃ carry out.
8, in accordance with the method for claim 1, it is characterized in that the described normal pressure that is reflected at carries out to the pressure of the vapour pressure of monohydroxy-alcohol.
9, in accordance with the method for claim 1, it is characterized in that having 10～22 carbon atoms in the fatty acid radical of described fatty acid glyceryl ester.
10, in accordance with the method for claim 1, it is characterized in that described vegetable raw material oil be soybean oil, rapeseed oil, sunflower seed oil, peanut oil, Oleum Gossypii semen, plam oil, Semen Lini oil, Viscotrol C, beet oil and sweet oil one or more; Animal raw materials fat can be lard, butter one or both.
11, in accordance with the method for claim 1, it is characterized in that described reaction employing continous way operation or batch operation, continous way operation hourly space velocity is generally 0.5～5h
-1, the batch operation the reaction time is generally 0.5～5h.
12, in accordance with the method for claim 1, it is characterized in that described reaction monohydroxy-alcohol and animal and plant fat or oily mol ratio are 3～50
13, in accordance with the method for claim 1, it is characterized in that described reaction monohydroxy-alcohol and animal and plant fat or oily mol ratio are 5～30.
14, in accordance with the method for claim 11, when it is characterized in that described employing batch operation, be benchmark with animal and plant fat or oil, the add-on of heterogeneous catalyst is 1%～30%.
15, in accordance with the method for claim 14, it is characterized in that described heterogeneous catalyst add-on is 5%～20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100464276A CN100360644C (en) | 2005-05-12 | 2005-05-12 | Production process of biological diesel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100464276A CN100360644C (en) | 2005-05-12 | 2005-05-12 | Production process of biological diesel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1861749A CN1861749A (en) | 2006-11-15 |
| CN100360644C true CN100360644C (en) | 2008-01-09 |
Family
ID=37389283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100464276A Active CN100360644C (en) | 2005-05-12 | 2005-05-12 | Production process of biological diesel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100360644C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338211B (en) * | 2007-07-03 | 2013-04-24 | 上海申旭特种机用燃料有限公司 | Method for preparing bio liquid fuel |
| CN101130163B (en) * | 2007-08-14 | 2010-05-19 | 西北农林科技大学 | Load type flyash solid base catalyst for producing biological diesel oil and method of producing the same |
| CN101289627B (en) * | 2008-06-10 | 2011-07-27 | 河南星火生物能源有限公司 | Process for reducing acid value of biodiesel |
| CN101993776B (en) * | 2009-08-27 | 2014-07-02 | 中国石油化工股份有限公司 | Method for deacidifying biodiesel |
| CN102908956B (en) * | 2011-08-01 | 2015-06-17 | 中国石油化工股份有限公司 | Esterification reactor and production method of dimethyl maleate |
| CN104560408B (en) * | 2013-10-23 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of production method of biodiesel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1654601A (en) * | 2005-02-24 | 2005-08-17 | 浙江工业大学 | Method for preparing biological diesel oil |
| CN1766040A (en) * | 2005-11-16 | 2006-05-03 | 张成岗 | Preparation method of biological diesel oil of plant oil fatty acid |
-
2005
- 2005-05-12 CN CNB2005100464276A patent/CN100360644C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1654601A (en) * | 2005-02-24 | 2005-08-17 | 浙江工业大学 | Method for preparing biological diesel oil |
| CN1766040A (en) * | 2005-11-16 | 2006-05-03 | 张成岗 | Preparation method of biological diesel oil of plant oil fatty acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1861749A (en) | 2006-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lotero et al. | The catalysis of biodiesel synthesis | |
| US7851643B2 (en) | Method of manufacturing fatty acid ethyl esters from triglycerides and alcohols | |
| CN101067091B (en) | Solid catalysis process of preparing biodiesel oil continuously with high acid value material | |
| CN101282921B (en) | Method for production of carboxylate alkyl esters | |
| US20070260078A1 (en) | Integrated process for the manufacture of biodiesel | |
| US8288573B2 (en) | Process for preparing a bio-diesel | |
| CN100360644C (en) | Production process of biological diesel | |
| US20120255223A1 (en) | process for conversion of low cost and high ffa oils to biodiesel | |
| CN100400622C (en) | Method of preparing biological diesel oil using solid base catalyst | |
| CN101591574B (en) | Method for preparing biodiesel by zirconia solid base catalyst | |
| CN101619329A (en) | Technical method for preparing biodiesel by biocatalysis one-pot method | |
| CN100537711C (en) | A kind of production method of biofuel | |
| CN102257108B (en) | Use of methanesulfonic acid for producing fatty acid esters | |
| CN100590176C (en) | Ester interchange method for producing bio-diesel oil | |
| CN1810932A (en) | Medium temperature and low pressure process to prepare biological diesel oil | |
| CN100460482C (en) | Method of preparing organism diesel oil from mixing plant oil | |
| CN1900224B (en) | Process for preparing biological diesel oil | |
| CN100526427C (en) | Method and catalyst for producing biological diesel oil by high-acid value grease | |
| CN1952048B (en) | Production process of biological diesel oil | |
| CN1952047B (en) | Production process of biological diesel oil | |
| CN101842471A (en) | The continuation method that is used for heterogenically catalyzed esterification of fatty acids | |
| CN1974724B (en) | High efficiency preparation process of biological diesel oil | |
| CN102993005A (en) | Method for preparing fatty acid alkyl ester by using long-chain alkyl sulfonic acid functional polyoxometalate as catalyst | |
| KR101072674B1 (en) | Process for the preparation of aliphatic alkylester | |
| CN103131540A (en) | Method for preparing biodiesel based on ionic liquid catalyzing peracid value rice bran oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |