CN101735845A - Method for separating and purifying biodiesel - Google Patents
Method for separating and purifying biodiesel Download PDFInfo
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- CN101735845A CN101735845A CN200810225728A CN200810225728A CN101735845A CN 101735845 A CN101735845 A CN 101735845A CN 200810225728 A CN200810225728 A CN 200810225728A CN 200810225728 A CN200810225728 A CN 200810225728A CN 101735845 A CN101735845 A CN 101735845A
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- 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
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- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention discloses a method for separating and purifying biodiesel. The method comprises the steps of: 1) performing degassing and distillation operation on a crude biodiesl product by a film evaporator to obtain the biodiesl of which the content of methyl ester is over 96 percent; and 2) performing alkaline soil deacidification on a product of separation treatment in the step 1) to obtain purified biodiesel of which an acid value satisfies the national standard. By the method, alkaline solution is absorbed on the surface of alkaline soil for a deacidification reaction, which effectively avoids emulsification; the method has simple operation conditions, does not need to strictly control conditions such as stirring and the like; components such as glycerol and soap can be absorbed after the reaction is finished; the obtained methyl ester does not need to be purified again, does not need to be dehydrated, is easy to separate, and has high yield; and a purified product has high quality. The method has the advantages of simple process flow, low equipment cost and energy consumption, and no wastewater pollution, and is suitable to be popularized and applied in a large area.
Description
Technical field
The present invention relates to the separation purification method of biofuel in the biological chemical field.
Background technology
Biofuel is to utilize renewable resources (for example culinary art wet goods of rape oil, soya-bean oil, recovery) to refine the clean fuel oil that forms.Biofuel has the characteristics of environmental friendliness, the use of alternative diesel oil as a kind of novel renewable energy, has worldwide obtained broad research and application.At present, biofuel is mainly used chemical method production, adopts vegetables oil and methyl alcohol or ethanol to carry out esterification under acid or basic catalyst and 230-250 ℃, generates corresponding fatty acid methyl ester or ethyl ester biodiesel.Now, the researchist also in the technology of research biological enzyme biodiesel synthesis, result of study shows that lipase is the catalyzer of the transesterification reaction of a kind of good catalytic alcohol and glycerin fatty acid ester.Enzyme has high catalytic efficiency and economy as a kind of biological catalyst, receives publicity day by day.
Result of study about separation phase in the production of biodiesel mainly contains:
The process for refining to the fatty acid methyl ester of chemical method production biofuel in document " Transesterification of vegetable oil biodieselusing heterogeneous base catalyst " such as B.K.Barnwal proposes, after reaction finishes, reclaim methyl alcohol, standing separation glycerine by distillation.The methyl esters layer is positioned at the upper strata, eliminates catalyzer and glycerine is residual by washing, carries out drying treatment with silica gel at last, obtains biofuel.
A.Froehlich mentions the production of carrying out biofuel by esterification in " Evaluation lf Camelina sativa oil as a feedstock forbiodiesel production ", leave standstill after reaction finishes and tell glycerine, utilize 1: 1 water of volume ratio that fatty acid methyl ester is carried out twice washing, reach the biofuel standard after the drying.
N.Usta points out for soot oil production biofuel in " Use of tobacco seed oil methyl ester in a turbocharged indirectin jection diesel engine ", wash by three times for the layer of methylester of fatty acid after the layering, and adding in the small amounts of phosphoric acid (2.5mL phosphoric acid/l fatty acid methyl ester) and residual catalyst in the washing for the first time, utilize 90 ℃ of following vacuum-dryings to slough residual moisture at last, obtain the biofuel product.
Filiz Karaosomanoglu etc. has studied the purge process of biofuel in " Investigation of the refining step of biodieselproduction ", utilize distilled water that product is made with extra care, studied the influence of the water of different acid and differing temps to washing effect, the result uses H
2SO
4(1: 1) is fit to the neutralization to biofuel, and the washing effect of 50 ℃ of warm water is best, and the finished product moderate purity can reach more than 99%.
R.Alcantara etc. are at " Catalytic production of biodiesel from soy-bean oil, usedfrying oil and tallow " in studied alkaline process production method of bio-diesel oil, main raw material has used soybean oil, frying waste oil and butter.Used hydrochloric acid soln (35%w/w) at separation phase, followed stirring, neutralized according to stoichiometric relation, stop to stir, after the layering, can obtain the biofuel of clear, the content of fatty acid methyl ester can reach more than 90% in the biofuel as a result.
Ayhan Demirbas etc. has studied the separation method of biofuel in " Biodiesel fuels from vegetable oils via catalytic andnon-catalytic supercritical alcohol transesterifications and other methods ", proposition is in the alkaline process catalyzed production biodiesel process, for guaranteeing that fatty acid methyl ester separates fully with glycerine, need leave standstill more than 20 hours, add the water of fatty acid methyl ester volume 5.5% subsequently, stir after five minutes, proceed the sedimentation of glycerine.Fatty acid methyl ester needs further washing after the sedimentation, needs continuous bubbling air in the process, and stirs, and finishes until the layer of methylester of fatty acid clarification.The biodiesel quality that obtains is very high, can reach international biofuel standard.
Hisamori etc. utilize waste cooking oil as the raw material production biofuel in " Biodiesel fuel produced from used cooking oil ", and separation method mainly is that washing separates glycerine from system.
Prawoto etc. adopt acid catalysis to prepare biofuel in " Bio formula to substitute diesel fuel ", reacted product is earlier at 65 ℃, 20～60mmHg pressure is evaporation 60～90min down, under similarity condition, distill 60min then, overhead product is a methyl alcohol, is that target product methyl esters purity is 99% at the bottom of the tower.
Jong Ho etc. adopt base catalysis method production biofuel in " Method for manufacturing biodiesel from edible oil ", the reaction back is by glycerine and soap in the thick product of centrifugation, distillation is evaporated methyl alcohol under 67 ℃ the condition being higher than, glycerine and soap remaining in the biofuel after adding Magnesium Silicate q-agent then and distilling form the solid bond thing, filter out solid matter at last.This technology do not have sewage to produce and technology simple.
Koerber etc. in " Impurity removal scheme for purification of fatty acid methylesters (biodiesel) obtained by transesterification " at first transesterificationization prepare fatty acid methyl ester, carry out purifying then, method is: (1) adds neutralizing agent and removes catalyzer in thick product; (2) adopt distillation method to remove methyl alcohol; (3) use starch phosphates and and the mixture absorption of urea remove glycerine.Suitable neutralizing agent comprises acid, acid anhydrides and salt (NaHCO for example
3) and CO
2
The Michael F pendant Lay of Washington, DC discloses patent " method and apparatus of refining biodiesel ", and after the transesterification after product left standstill, the product alkyl ester formed the upper strata, and it is by decant and through purification step, to remove particulate matter and alkyl alcohol from the product alkyl ester; And lower floor's product glycerine is discharged out.The purification of product alkyl ester preferably includes, and makes the product alkyl ester through top water spray washing in washing tank, injects stream of air bubbles simultaneously.
The people such as BS Cook of dallas, u.s.a group public affairs disclose patent " making with extra care of the biofuel of employing sorbent material ", this is the method that makes biodiesel fuel and at least a sorbent material such as Magnesium Silicate q-agent contact treating biodiesel fuel, this method is removed the impurity that generates at the biodiesel fuel production period, as soap.
People such as the Chen Guan of University Of Tianjin benefit utilize waste oil production biofuel (CN1670128), after reaction finishes, with rotary centrifuge the glycerine of bottom and the methyl esters on upper strata are separated, afterwards methyl esters is washed, remove residual catalyzer, soap, methyl alcohol and other water soluble components, dry then, store, methyl esters can distill under vacuum to obtain higher purity.
People such as the Chen Denglong of Fujian Normal University utilize microwave method to prepare biofuel (CN1810931), at first steam unreacted methanol, leave standstill to obtain the upper strata coarse biodiesel in 12 hours, with containing 10%NaCO
3Saturated aqueous common salt in and the washing coarse biodiesel, obtain neutral crude product biofuel, further adopt continous vacuum distillatory method, the cut between collecting 130 ℃-190 ℃ under the vacuum 5mmHg obtains refined biometric diesel oil.
Open biofuel primary products that magnitude people not produces finished product (CN1818028) through separating methanol, washing back, drying and dehydrating, refining processing back generation biofuel.
People such as Yang Jinliang disclose patent " water distilling apparatus of production biofuel " and " production method of biofuel and distillation tower ", wherein methyl alcohol direct heating in reactor steams recovery, washing process is still arranged afterwards, enter the distillation tower distillation after the dehydration, distillation temperature is 180-270 ℃.
The Cheng Fangding of Henan Province Shangqiu Fat Chemicals Factory discloses patent " the vertical film flash rectifying still in a kind of production of biodiesel " and " application of vertical film flash distillation rectifying process in production of biodiesel ", this equipment mainly is made up of rectifying tower still and thin-film evaporator, the present invention can significantly reduce the residence time of thick methyl esters in rectifying still, less polyreaction, less oil loss is more than 10%, heat utilization efficiency can improve more than 8%, has reduced energy consumption cost.
People such as the Lv Bo of Henan Zhongying Yuding Science and Technology Co., Ltd. disclose patent " utilize low temperature prepares method of bio-diesel oil and special-purpose distillation tower in the plants fruits and seeds oil ", and technology is that the mixture after the transesterify enters separating tank, isolates coarse biodiesel and raw glycerine; Isolated coarse biodiesel enters special-purpose distillation tower and distills purification, and the biofuel after the vaporization enters the processed oil hold-up vessel after the supercooler cooling, and distillation test residue generates plant asphalt, enters the plant asphalt hold-up vessel.This invention adopts special-purpose distillation tower to distill, and has optimized the traditional batch distillation and the equipment of continuous still battery.
People's publications " utilizing reactive separation process coupling technique to prepare the processing method of biofuel " such as the Wang Jin of Tsing-Hua University good fortune according to the PROCESS COUPLING principle, are researched and developed out the continuous operation process that catalytic reaction process and product sepn process are coupled.Separating technology separates low-carbon alcohol for using rectifying tower, and glycerine further utilizes both density differences to separate by separator with ester.
The leaf activity of Longyan Zhuoyue New Energy Development Co., Ltd. discloses patent " continuous rectification apparatus for biological diesel oil ", the above rectifying tower of this process using two-stage, process unit avoided biofuel cracking, fatty acid separation not thoroughly, problem such as oxidation, color and luster be dark, energy consumption is low, has realized the effective separation between moisture content, fatty acid methyl ester, the mink cell focus.
The Zhu Baozhang of South China Science ﹠ Engineering University also discloses patent " utilizing rectifying tower or distillation tower purification production method of bio-diesel oil ", technology is that esterification afterreaction product leaves standstill or high speed centrifugation gets thick methyl esters, carry out rectifying tower or distillation tower again and purify, finally obtain methyl esters content in the biofuel more than 98%.
People such as the Wang Xingguo of Southern Yangtze University prepare biofuel (CN1821349) with the edible oil processing fent, transesterification reaction finishes the back and adopts 0.01MPa, and 60 ℃-70 ℃ following thin-film evaporators reclaim solvent, standing demix then, the upper strata is the methyl esters phase, and lower floor is a glycerine and the dissolving each other mutually of water.Methyl esters is proceeded to handle mutually, and the methyl esters that the deodorization gold-plating goes out after the thing esterification adopts 40 ℃ of-60 ℃ of hot washes 2 times mutually, carries out molecular distillation then, and at 1-5Pa, 120 ℃-140 ℃ are separated acquisition purity down in the biofuel more than 99%.
Shao's equality people of HeFei University of Technology utilization molecular distillation technique in " the molecular distillation separating technology of biofuel research in the rape seed oil deodorization distillate " separates synthetic biofuel in the rapeseed oil deodorization distillate, investigated of the influence of the operating parameters of molecular distillation to the biofuel rate of recovery, result of study shows: when system pressure is 5.3Pa, 120 ℃ of generating surface temperature, 70 ℃ of feeding temperatures, knifing rotating speed 150r/min, during feeding rate 120mL/h, the biofuel rate of recovery reaches 41g/100mL, and fatty acid methyl ester is more than 89%.
The Zhu Baozhang of South China Science ﹠ Engineering University discloses a series of patents about molecular distillation production biofuel, comprise " directly utilizing molecular distillation technique production method of bio-diesel oil ", " utilizing molecular distillation technique production method of bio-diesel oil ", " utilizing centrifugal type technique of molecular distillation to produce the oil engine method of bio-diesel oil ", " centrifugal molecular distillating process of producing of biological diesel for automobile ", all be to adopt after the esterification thick product directly to enter molecular distillation to carry out bi-level treatment, the one-level degassing, one-level steams methyl esters.This method has been omitted washing and drying process, and technical process is simple, does not have contaminated wastewater, saves the water treatment expense.
Du Xiaoxing discloses patent " biodiesel oil multiple-grade molecular distillation process and device thereof ", and wherein the first step is for removing low component materials, the component of the different boiling ranges of collections at different levels afterwards, and distillation progression is 2≤n≤6 grade.
People such as Dong Qinghua disclose patent " a kind of production method and producing apparatus that utilizes molecular distillation technique production biofuel ", technology be biodiesel raw material with acid and methyl alcohol by certain ratio high speed premix, the pre-esterification reactor degassing in efficient rotary film evaporator then, carry out continuous short-path distillation free fatty acids at short-distance distiller, depickling forms fatty acid ester, and distills out methyl alcohol and glycerine.Its characteristics are that technology is simple, the no three wastes, reduce cost, and speed is fast, productivity height, suitable large-scale industrial production.
Guangxi Normal University's publication " technique for preparing biological diesel oil by microwave catalyzing and film separating " is used the membrane sepn biofuel, and technology is simple, and energy consumption is low, but the particular case of not mentioned film.
Yang Yifang discloses patent " distillation-free preparation of biological diesel oil ", it is characterized in that adopting the temperature distribution, at first by being reduced to 0 ℃, isolates glycerine; Remaining liq is heated to 70-80 ℃, evaporates methyl alcohol.Adopt fusing point boiling point bound energy to simplify the purification and separation process of biofuel like this.
People such as the Hou Xianglin of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences disclose patent " method of super critical extracting and rectifying biological diesel oil ", this method is that the biofuel crude product is made with extra care by supercritical extraction, remove catalyst residue, phosphatide, glycerine, sterol in the biofuel, simultaneously remove other glyceryl ester, compare and to cut down the consumption of energy with reduced pressure distillation technique in conjunction with supercutical fluid rectifying adsorption technology.
By above content as can be seen, the research of chemical method separation and purification biodiesel processes is comparatively deep, mainly be to adopt washing or two kinds of main method of rectifying that the biofuel product is separated purification, these have certain reference for immobilized enzyme production biofuel, but also have bigger difference from essence.In addition, adopt method for washing to be difficult to impurity is thoroughly removed, also can take the part methyl esters out of on the contrary, reduce productive rate; Adopt the method for washing also can produce a large amount of waste water, also can waste water resource when producing environmental pollution; The drying process that adopts the washing back to be increased has increased equipment and processing cost; In institute's research direction, underpressure distillation has still accounted for very big proportion, especially based on rectifying and molecular distillation.But can not deny that common distillatory efficient is on the low side, and rectifying and molecular distillation technology are all relatively large on equipment cost and energy consumption; In other new separating technology, membrane sepn, extraction process, non-evaporatingly heat up in a steamer technology or the sorbent material method all has certain novelty, and simple to operate, there was not high energy consumption, but these method material costs are generally higher, whether can expand industrialization to, also do not come to a conclusion.
The production of biofuel should have standard to guarantee that as instructing its quality, normalise simultaneously also are essential condition of the market access, and the development of biofuel is stimulating the biofuel establishment of standard.Austria had formulated in the world that first is the biofuel standard of benchmark with the rapeseed methylester in 1992, and very fast Germany (EDIN 51606), France, Czech and the U.S. (ASTM PS-121) have also set up biofuel standard separately respectively.Biofuel can be made by different material, the raw material difference, thereby the standard of various countries also exists some differences, wherein strict with German standard.China has also put into effect tentative standard in May, 2007, and it has made detailed regulation to 16 specific targets and examination criteria.Wherein, the requirement to acid number is very important one.
Alkali cleaning is classical deacidifying process, lot of domestic and international research is carried out neutralization reaction with alkaline solutions such as sodium hydroxide and free fatty acids, the gained fatty acid sodium salt is separated from oil product, obtain free lipid acid through acidifying, reaction process can be finished in moment, but was easy to generate emulsion in reaction process.And alkali lye runs off in a large number in company with converted products, and sodium hydroxide reagent can not be regenerated, and the sodium salt that separation of fatty acids generated is seriously polluted; With aqueous ammonia to replace caustic alkali lipid acid is extracted from oil phase, come down to lipid acid is converted into ammonium salt, from oil product, separate, the ammonium salt thermal degradation discharges ammonia and reclaims lipid acid simultaneously, but cost is higher, and the solvent recuperation energy consumption is higher, and depickling oil colours degree is subjected to certain influence; With calcium oxide, calcium sulphonate or other metal oxide, and an alkali metal salt of small molecular organic acid equally can depickling, but also has a large amount of alkaline residues and the problem of saline sewage of producing.
People such as Tang Xiaodong (1997,2005,2006) adopt selective solvent, also can extract lipid acid as ethanol etc. from diesel oil, and document points out that formyl replaces dimethylamine, acetonitrile, industrial triglycol etc. can slough petroleum acid in the oil effectively as extraction solvent.But its selectivity is not high, and the ethanol consumption is big, need to adopt the multi-stage countercurrent extracting, and recovery system is also comparatively complicated, and energy consumption is bigger, also is the one of the main reasons that limits the further industrial application of this class isolation technique.
Li Shuzhen etc. (1995) utilize hydro carbons and petroleum acid also can separate lipid acid in the diesel oil oil to the difference of some adsorbents adsorb ability, the sorbent material that is adopted comprises natural inorganic sorbents, as clay, kaolin, bauxite or natural silica gel etc., and synthetic sorbent material, as zwitterion sorbent material or strong alkali ion exchange resin etc., whole technological process bulky complex, invest higher, these have all limited adsorption method of separation in industrial application, are applied to the research of laboratory to petroleum acid structure and composition at present more.
People such as Huang Mingfu (2003) have reported that the use microwave irradiation carries out depickling in " straight-run diesel oil depickling Study on new method under the microwave ", but still need to use NaOH to make de-acidying agent, and there is emulsification in profit, the process cost height.
People such as Liu Dachuan (2001) have studied the distillation method depickling, and are different with the FFA relative volatility by means of triglyceride level, under the condition of high vacuum, distill out the FFA in the grease, to reduce the process of the FFA in the grease.Method commonly used has wet distillation and molecular distillation etc.The shortcoming of steam distillation depickling is too dark with regard to the finished product oil colours, needs decolouring again.
People such as Raman (1991) have studied membrane sepn depickling method, according to the difference of methyl esters and FFA molecular weight size, can utilize membrane separation technique that the FFA in the grease is effectively separated.But also there are some difficulties in the industrialization of membrane separation technique depickling, and at first because the lipid molecule amount is all very little, during as if usefulness nanofiltration and reverse osmosis, filtration velocity is low, and film is contaminated easily again, film occurs and stops up; Secondly, membrane sepn cost height, and methyl esters is close with the fatty acid molecule amount, is difficult to eliminate.
People such as Wang Yong (2001) have studied urea adduct method, urea adduct method is a kind of fatty acid separation method commonly used, its principle is that urea molecule can form more stable crystal inclusion compound with saturated fatty acid or monounsaturated fatty acids and separates out in crystallisation process, and polyvalent unsaturated fatty acid is because two key is more, the carbochain bending, have certain sterie configuration, be difficult for, adopt the filtering method can be dissimilar fatty acid separation by urea clathration.
As seen, traditional and present method is all existing certain problem aspect the processing acid number.At present, the production technique of the producer of domestic most production biofuel employing exists the problem that the production cycle is long, product purity is lower, the rate of recovery is not high, cost is higher and pollution is more serious.Do not reach the requirement that the fatty acid methyl ester of discharging standard biological diesel oil such as IV in Europe reaches more than 98% and pollutant emission is limited the quantity of from quality and environmental protection, therefore can not can only be confined to Industrial Boiler, farm machinery etc. and require relatively low industry field as the substitute energy of high-grade car; On the other hand, consider that from the cost angle completion rate that higher equipment and energy cost are lower in addition makes the market competitiveness not strong.
Summary of the invention
The invention provides a kind of separation purification method of biofuel easy and simple to handle, with low cost.
The separation purification method of biofuel provided by the present invention can may further comprise the steps:
1) with thin-film evaporator the thick product of biofuel is outgased and distillation procedure, obtain methyl esters content in the biofuel more than 96%;
2) product after the step 1) separating treatment is carried out the alkaline soil depickling, obtain the purified biofuel that acid number meets national standard.
In the separation purification method of above-mentioned biofuel, the thick product of biofuel in the described step 1) is vegetables oil, animal oil, microbial oil or trench wet goods stock oil and methyl alcohol at lipase-catalyzed esterification reaction product after carrying out esterification down, by leaving standstill or high speed centrifugation obtains after removing by-product glycerin.
Described thin-film evaporator comprises falling-film evaporator and rotor segment formula thin-film evaporator.
Described step 2) alkaline soil in is alkaline wilkinite or zeolite powder, available from the gloomy mill house of Xinyang, Henan industry city China.
Specifically, described step 1) may further comprise the steps:
A) at first carry out esterification and obtain the thick methyl esters of biofuel,, collect supernatant liquor and obtain the thick product of biofuel by leaving standstill or high speed centrifugation removal by-product glycerin (subnatant) by lipase-catalyzed stock oil and methyl alcohol;
B) the thick product that step a) is obtained by falling-film evaporator vacuum tightness-0.06～-operation outgases under the 0.08MP, 90 ℃～120 ℃ conditions of temperature, remove falling-film evaporator upper outlet component (low boiling components such as the water in the thick product, methyl alcohol), the outlet component is carried out next step operation under collecting;
C) product after will outgasing (outlet component down) carries out distillation procedure by rotor segment formula thin-film evaporator under pressure 60～130Pa, 160 ℃～180 ℃ of hot face temperature, scraper plate rotating speed 130～140rpm condition, collect rotor segment formula thin-film evaporator light component outlet (upper outlet) product, obtain methyl esters content in the biofuel more than 96%.
The step of specifically, described step 2) product after the step 1) separating treatment being carried out the alkaline soil depickling can may further comprise the steps:
A) by the acid number of GB GB/T 264 methods detection step 1) product, obtain the acid number of methyl esters content in the biofuel more than 96%;
B) calculate the consumption that removes the required saturated basic solution of lipid acid according to the solubleness of alkaline matter when differing temps (20-90 ℃) by acid number, and by acid number: the alkaline soil mass ratio is 1: the ratio of 0.5-5 is calculated native consumption;
C) alkaline soil and saturated basic solution are mixed under heat-retaining condition, form the alkaline soil de-acidying agent;
D) under heat-retaining condition, the mixture and the methyl esters content of step c) is mixed in the biofuel more than 96%;
E) in temperature 30-90 ℃ water-bath, react 20-40min under the mixing speed 100-1000rpm condition, after removing solid matter, centrifugal or filtration obtains the purified biofuel that acid number meets national standard.
In the step of above-mentioned concrete alkaline soil depickling, the selection of the saturated alkaline matter in the step b) is diversified, as Na
2CO
3, NaHCO
3, Na
2SO
3, NaOH, KOH etc. be alkalescence salt or the saturated solution of alkali all can.
For obtaining reaction effect preferably, after stopping, the step e) reaction also need insulation again to leave standstill 5-60min.
In addition, for better reclaiming alkaline soil and obtaining maximum economic benefits, also can carry out acidification to the alkaline soil de-acidying agent after using, method is: at 30-90 ℃, use acid treatment 15-60min under the condition of 100-500rpm.Described acid is preferably strong acid such as sulfuric acid, hydrochloric acid.
The application of specific acid stripping method in biodiesel manufacture that more than relates to also belongs to content of the present invention.
Biofuel with the aforesaid method separation and purification also belongs to protection scope of the present invention.
The invention provides a kind of separation purification method of biofuel.This method employing thin-film evaporator (falling-film evaporator and rotor segment formula thin-film evaporator) and alkaline soil depickling and modified technology are carried out the separation and purification of biofuel, obtain meeting the biofuel product of Germany (EDIN 51606), France, the U.S. (ASTM PS-121) and People's Republic of China's national standards such as (GB/T20828-2007).Outstanding characteristics of the present invention are basic solution to be adsorbed in the alkaline soil surface carry out the depickling reaction, effectively avoid emulsification, operational condition is simple, do not need conditions such as strict control stirring, reaction finishes to adsorb compositions such as glycerine and soap, and the gained methyl esters does not need purifying once more, need not dewater, and be easy to separate, the yield height, and alkaline soil is cheap and easy to get.
It is the technology that stock oil prepares biofuel that the present invention can cooperate existing vegetables oil, animal oil, microbial oil or sewer oil cheap and easy to get, after further simplifying separation purifying technique, not only reduce the production cost of biofuel, and can obtain purity height, the qualified high-quality biofuel finished product of acidity value; A whole set of enzyme catalysis working system furthermore separation purifying technique has solved the environmental problem of industrial wastewater pollution, makes it to become fully green, environment-friendly type biodiesel production technique.It is simple that the present invention has technical process, and equipment cost and energy consumption are low, and do not have the advantage of contaminated wastewater, suits large area to popularize and use.
Below in conjunction with specific embodiment the present invention is described in further details.
Description of drawings
Fig. 1 is the process flow sheet of separating and purifying biodiesel method of the present invention
Embodiment
The present invention separates method with purifying to the existing thick product of biofuel.Fig. 1 shows with the present invention and carries out the separation of biofuel, the process of purifying, wherein the thick product of biofuel through falling film evaporation, scraper plate evaporation after again by the alkaline soil depickling, obtain the biofuel that acid number behind the purifying meets national standard.Among the present invention, the falling-film evaporator that uses, scraper evaporator and other treatment unit are conventional equipment, and the reagent of use also is conventional reagent, and the special alkaline soil that uses is alkaline wilkinite or zeolite powder available from the gloomy mill house of Xinyang, Henan industry city China.The thick product of object organisms diesel oil of separation and purification treatment of the present invention, it can be the product (main component is crude fatty acid methyl ester and glycerine) that the reaction of lipase-catalyzed stock oil and methanol esterification obtains, the preparation of the thick product of this biofuel (is published in " modern chemical industry " the 23rd the 9th phase of volume referring to document " biodiesel production by immobilized lipase ", in September, 2003, the author: Nie Kaili Wang Fang Tan Tian is big), also can be the further separation of needs of other method acquisition and the thick product of biofuel of purifying.
Method therefor is ordinary method if no special instructions among the following embodiment.
The separation of embodiment 1, biofuel, purifying
Concrete grammar may further comprise the steps:
1) separation and purification: with thin-film evaporator the thick product of biofuel is outgased and distillation procedure, obtain methyl esters content and be 96% biofuel:
A) separation and purification object: lipase-catalyzed soybean oil (stock oil) is reacted the thick product of biofuel that obtains with methanol esterification, by leaving standstill or high speed centrifugation removal by-product glycerin (subnatant), collect supernatant liquor (main component is a crude fatty acid methyl ester) as next step separation and purification object;
B) falling film evaporation: the supernatant liquor that step a) is obtained is by the falling-film evaporator operation that outgases under vacuum tightness-0.06MP, 120 ℃ of conditions of temperature, remove falling-film evaporator upper outlet component (low boiling components such as the water in the thick product, methyl alcohol), the outlet component is carried out next step operation under collecting;
C) scraper plate evaporation: the product after the step b) degassing (outlet component down) is carried out distillation procedure by rotor segment formula thin-film evaporator under pressure 90Pa, 170 ℃ of hot face temperature, scraper plate rotating speed 130rpm condition, collect rotor segment formula thin-film evaporator light component outlet (upper outlet) product.
Detect with the methyl esters content of vapor-phase chromatography, obtain methyl esters content and be 96% biofuel the step 1) product.
2) depickling: the product after the step 1) separating treatment is carried out the alkaline soil depickling, obtain the purified biofuel that acid number meets national standard:
A) detect methyl esters content that step 1) obtains in 96% biofuel according to State Standard of the People's Republic of China GB/T 264 methods, acid number is a 10mgKOH/g oil as a result;
B) according to alkaline matter (NaHCO
3, Na
2SO
3, NaOH or KOH etc. be alkalescence material all can) solubleness when differing temps (20-90 ℃), calculate the consumption that removes the required saturated basic solution of lipid acid by acid number; In addition, in acid number: soil is 1: the ratio of 0.5-5 is calculated the consumption of alkaline soil;
The solubleness (g/100g water) of table 1 differing temps lower section alkaline matter
Na during c) with 20 ℃ of 12g carrier alkaline soil and 10g
2CO
3Saturated basic solution mixes under heat-retaining condition; Form the alkaline soil de-acidying agent;
D) under heat-retaining condition, the alkaline soil de-acidying agent and the 160g methyl esters content of step c) is mixed in the biofuel more than 96%;
E) at 60 ℃ of bath temperatures (30-90 ℃ all can), react 30min (20-40min all can) under motor mixing speed 550rpm (the 100-1000rpm all can) condition, filter or the centrifugal solid matter of removing, obtain the purified biofuel 148g that acid number meets national standard, be the finished product of the present invention.The depickling step rate of recovery was 92.7% (theoretical value is about 95%).
Product is carried out every index detect, product performance are as shown in table 2.
Table 2 product index performance test results
| Project name | Analytical data | Unit | Standard | Standard figures |
| Density (20 ℃) | ??869 | ??(kg/m 3) | ??GB/T?2540 | ??820-900 |
| Kinematic viscosity (40 ℃) | ??3.95 | ??mm 3/s | ??GB/T?265 | ??1.9-6.0 |
| Flash-point (remaining silent) | ??＞170 | ??℃ | ??GB/T?261 | Be not less than 130 |
| Cold filter clogging temperature (adjusting the back) | ??-17 | ??℃ | ??IP?309 | ??---- |
| Sulphur content (massfraction) | ??0.0005 | ??％ | ??IP?309 | Be not more than 0.005 |
| Acid number | ??0.4 | ??mgKOH/g | ??GB/T?264 | Be not more than 0.8 |
| Methyl esters content (massfraction) | ??＞98％ | ??％ | Gas-chromatography | ??---- |
| Cetane value | ??73.6 | ??GB/T?386 | Be not less than 49 | |
| Water-content (massfraction) | ??0.029 | ??％ | ??SH/T?0246 | Be not more than 0.05 |
| Project name | Analytical data | Unit | Standard | Standard figures |
| Copper corrosion (50 ℃, 3h) | ??1 | Level | ??ASTM?D130 | Be not more than 1 |
| Total glycerol content (massfraction) | Do not detect | ??％ | ??ASTM?D6584 | Be not more than 0.240 |
Embodiment 2-5, use of the separation and purification of different de-acidying agents to biofuel
The method identical with embodiment 1 wherein, changes the consumption of basic solution and alkaline soil, obtains the purified biofuel that acid number meets national standard respectively.The result is referring to table 3.
Table 3 example 2-5 result
| Changing factor | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The alkali dissolution temperature (℃) | ??20 | ??40 | ??50 | ??60 |
| Basic solution and consumption | ??NaOH??2.3g | ??Na 2SO 3??6.7g | ??KOH??3.06g | ??NaHCO 3??17.4g |
| Alkaline soil consumption (1: 0.5-5) | ??11.5g(1∶5) | ??20.1(1∶3) | ??1.53g(1∶0.5) | ??26g(1∶1.5) |
| The rate of recovery (theoretical value about 95%) | ??92.5％ | ??93.4％ | ??91.3％ | ??93.7％ |
| Product water-content (massfraction) | ??0.033％ | ??0.019％ | ??0.039％ | ??0.040％ |
| Total glycerol content | Do not detect | ??0.05％ | Do not detect | ??0.003 |
| Acid number (mgKOH/g) | ??0.47 | ??0.50 | ??0.54 | ??0.51 |
| Methyl esters content | ??＞98％ | ??＞98％ | ??＞98％ | ??＞98％ |
Embodiment 6-9, to separation, the purifying of the biofuel of different material
As shown in Figure 1, carry out separation, the purifying of biofuel with method of the present invention, concrete grammar is identical with embodiment 1, and difference is to change the stock oil of producing thick methyl esters, and purified biofuel important indicator is referring to table 4.
Table 4 example 6-9 result
| Project name | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Produce the stock oil of thick methyl esters | Acidifying oil | Sewer oil | Rapeseed oil | Oleum Verniciae fordii |
| The parameter of rotor segment formula thin-film evaporator | 160 ℃ of scraper plate rotating speeds of vacuum 60Pa temperature 130rpm | 180 ℃ of scraper plate rotating speeds of vacuum 130Pa temperature 135rpm | 165 ℃ of scraper plate rotating speeds of vacuum 70Pa temperature 140rpm | 175 ℃ of scraper plate rotating speeds of vacuum 110Pa temperature 130rpm |
| Density (20 ℃) | ??842 | ??874 | ??856 | ??847 |
| Kinematic viscosity (40 ℃) | ??3.21 | ??3.92 | ??2.78 | ??3.45 |
| Flash-point (remaining silent) ℃ | ??154 | ??167 | ??173 | ??158 |
| Cold filter clogging temperature/℃ (adjusting the back) | ??-17 | ??-16 | ??-17 | ??-17 |
| Sulphur content (massfraction) | ??0.0005％ | ??0.0024％ | ??0.0032％ | ??0.0003％ |
| Acid number (mgKOH/g) | ??0.40 | ??0.47 | ??0.45 | ??0.50 |
| Methyl esters content | ??＞98％ | ??＞98％ | ??＞98％ | ??＞98％ |
| Cetane value | ??56.6 | ??69 | ??70.1 | ??66.5 |
| Water-content (massfraction) | ??0.031％ | ??0.014％ | ??0.007％ | ??0.015％ |
| Copper corrosion (50 ℃, 3h) | 1 grade | 1 grade | 1 grade | 1 grade |
| Total glycerol content | Do not detect | ??0.14％ | ??0.17％ | Do not detect |
Using the same method also to be that the thick methyl esters of stock oil carries out separation and purification to plam oil, Oleum Gossypii semen, sunflower seed oil, peanut oil, sweet oil, oleic acid, linolic acid, linolenic acid, stearic acid, palmitinic acid, obtains the purified biofuel that acid number meets national standard equally.
In above embodiment, acidification can be carried out so that recycling for the precipitation of separating after the depickling processing (reactant of alkaline soil and absorption).Acidation treatment method is: at 30-90 ℃, use acid treatment 15-60min under the condition of 100-500rpm.Described acid is preferably strong acid such as sulfuric acid, hydrochloric acid.
Claims (10)
1. the method for a separating and purifying biodiesel may further comprise the steps:
1) with thin-film evaporator the thick product of biofuel is outgased and distillation procedure, obtain methyl esters content in the biofuel more than 96%;
2) product after the step 1) separating treatment is carried out the alkaline soil depickling, obtain the purified biofuel that acid number meets national standard.
2. method according to claim 1 is characterized in that: the thick product of the biofuel in the described step 1) is the esterification reaction product after vegetables oil, animal oil, microbial oil or trench wet goods stock oil and methyl alcohol carry out esterification; Described thin-film evaporator comprises falling-film evaporator and rotor segment formula thin-film evaporator.
3. method according to claim 2, it is characterized in that: described with thin-film evaporator to the thick product of biofuel outgas and distillation procedure before, also comprise the thick product of biofuel is left standstill or high speed centrifugation is removed the step of byproduct, obtain thick methyl esters.
4. according to claim 1 or 2 or 3 described methods, it is characterized in that: described step 1) may further comprise the steps:
A) with thick methyl esters by the falling-film evaporator operation that outgases;
B) product after will outgasing distills by rotor segment formula thin-film evaporator, obtains methyl esters content in the biofuel more than 96%.
5. according to the arbitrary described method of claim 1 to 4, it is characterized in that: described step 2) product after the step 1) separating treatment is carried out the alkaline soil depickling and may further comprise the steps:
A) detect the acid number of the methyl esters content of step 1) acquisition in the biofuel more than 96%;
B) calculate the consumption of saturated basic solution according to the solubleness of alkaline matter 20-90 ℃ the time by acid number, and in acid number: alkaline soil is 1: the ratio of 0.5-5 is calculated the consumption of alkaline soil;
C) alkaline soil and saturated basic solution are mixed formation alkaline soil de-acidying agent under heat-retaining condition;
D) under heat-retaining condition, the alkaline soil de-acidying agent and the methyl esters content of step c) is mixed in the biofuel more than 96%, stir also reaction 20-40min;
E) remove solid matter, obtain the purified biofuel that acid number meets national standard.
6. method according to claim 5 is characterized in that: the saturated basic solution in the described step b) is Na
2CO
3, NaHCO
3, Na
2SO
3, NaOH or KOH saturated solution.
7. according to claim 5 or 6 described methods, it is characterized in that: temperature described step 2) is 30-90 ℃, and the step d) mixing speed is 100-1000rpm; After stopping, reaction also need insulation again to leave standstill 5-60min.
8. method according to claim 5 is characterized in that: the solid matter that step e) is removed carries out acidification, and method is: at 30-90 ℃, use acid treatment 15-60min under the condition of 100-500rpm, described acid is sulfuric acid or hydrochloric acid.
9. the acid stripping method in the biodiesel manufacture is characterized in that: by the arbitrary described depickling step of claim 5 to 8.
10. use the biofuel of each described method separation and purification of claim 1-9.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071109A (en) * | 2011-01-15 | 2011-05-25 | 青岛福瑞斯生物能源科技开发有限公司 | Method for decoloring biodiesel prepared from illegal cooking oil |
| CN102533443A (en) * | 2011-12-30 | 2012-07-04 | 代洪达 | Method for refining cracking biodiesel to fuel oil of internal combustion engine |
| CN104419456A (en) * | 2013-08-27 | 2015-03-18 | 丹阳市助剂化工厂有限公司 | Refining method and refining apparatus of high-quality biodiesel |
| CN108069828A (en) * | 2018-01-09 | 2018-05-25 | 山东福富新材料科技有限公司 | A kind of production biodiesel byproduct crude glycerin high-purity purification technique |
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| CN113789445A (en) * | 2021-07-29 | 2021-12-14 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for regenerating ineffective gallium and germanium extractant by organic phase separation |
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2008
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071109A (en) * | 2011-01-15 | 2011-05-25 | 青岛福瑞斯生物能源科技开发有限公司 | Method for decoloring biodiesel prepared from illegal cooking oil |
| CN102071109B (en) * | 2011-01-15 | 2013-05-01 | 青岛福瑞斯生物能源科技开发有限公司 | Method for decoloring biodiesel prepared from illegal cooking oil |
| CN102533443A (en) * | 2011-12-30 | 2012-07-04 | 代洪达 | Method for refining cracking biodiesel to fuel oil of internal combustion engine |
| CN102533443B (en) * | 2011-12-30 | 2013-12-04 | 代洪达 | Method for refining cracking biodiesel to fuel oil of internal combustion engine |
| CN104419456A (en) * | 2013-08-27 | 2015-03-18 | 丹阳市助剂化工厂有限公司 | Refining method and refining apparatus of high-quality biodiesel |
| CN110088234A (en) * | 2016-11-22 | 2019-08-02 | Rj 利格鲁普公司 | The method of separation pyrolyzing oil |
| CN108069828A (en) * | 2018-01-09 | 2018-05-25 | 山东福富新材料科技有限公司 | A kind of production biodiesel byproduct crude glycerin high-purity purification technique |
| CN113789445A (en) * | 2021-07-29 | 2021-12-14 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for regenerating ineffective gallium and germanium extractant by organic phase separation |
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