CN102071108B - Preparation method of biodiesel - Google Patents
Preparation method of biodiesel Download PDFInfo
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- CN102071108B CN102071108B CN200910238264A CN200910238264A CN102071108B CN 102071108 B CN102071108 B CN 102071108B CN 200910238264 A CN200910238264 A CN 200910238264A CN 200910238264 A CN200910238264 A CN 200910238264A CN 102071108 B CN102071108 B CN 102071108B
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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
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Abstract
The invention provides a preparation method of biodiesel, comprising the following steps of: (1) undergoing a contact reaction of oil and monohydric alcohol in the presence of a base catalyst to ensure that the conversion rate of the oil is up to 80-95 percent by weight; (2) separating a glycerol phase and a light oil phase from a product obtained in the step (1); (3) contacting the light oil phase obtained in the step (2) with the monohydric alcohol and the base catalyst in the presence of the base catalyst in the presence of the base catalyst to ensure that the conversion rate of the oil is up to over 98 percent by weight; and (4) separating the contacted product obtained in the step (3) to obtain the biodiesel and the monohydric alcohol, and recycling the obtained monohydric alcohol. The method provided by the invention has the advantages of increasing the balance conversion rate of the oil, reducing the contents of triglyceride and diglyceride in the product and ensuring that the contents of free glycerol and total glycerol in the biodiesel product meet the requirement of the national standard.
Description
Technical field
The invention relates to a kind of preparation method of biofuel.
Background technology
Biofuel is a kind of long chain fatty acid ester, mainly refers to fatty acid methyl ester on the industrial application.It is to obtain through animal and plant grease and monohydroxy-alcohol transesterification reaction.At present the technology of popular production biofuel mainly is with highly basic such as KOH, NaOH, NaOCH
3Deng being catalyzer, be the principal reaction device with still formula, CSTR etc.Because the not mutual solubility of grease and methyl alcohol stirs the mass-transfer efficiency of promoting grease and monohydroxy-alcohol through strengthening mostly in the industry, thereby improves transesterification reaction speed, has increased energy consumption but strengthen to stir.In addition; Because generating biofuel through transesterify, grease divide the consecutive reversible reaction of three steps to carry out; The existence of intermediate product monoglyceride and triglyceride and unconverted triglyceride level all influences the quality of product, should take measures to make its content to be reduced within the scope of standard-required.
How to improve the transformation efficiency of grease triglyceride level, promote intermediate product monoglyceride and triglyceride to be converted into the focus place that biofuel is the biofuel new technology development as far as possible.CN1710026A discloses the process method that a kind of heterogeneous catalysis transesterification reaction prepares biofuel; Under 140-250 ℃ temperature of reaction; When carrying out transesterification reaction, product fatty ester and glycerine are separated from reaction system through round-robin monohydroxy-alcohol gas; In reaction process, realize separating of product fatty ester and raw oil material and intermediate product triglyceride and monoglyceride, realized the coupling of reaction and sepn process, improved the speed of heterogeneous catalytic reaction; And realized the separation of product simultaneously, reduced production cost and the throughput that has improved equipment effectively.Yet this method methanol consumption amount is big, and it is high to reclaim the methyl alcohol energy consumption, and fatty acid ester product acid number that obtains and glycerol content height, can not satisfy the requirement of quality standard.
Summary of the invention
To the objective of the invention is that the energy consumption that existing method for producing biodiesel exists is higher in order overcoming, the biofuel quality product is not easy shortcoming up to standard, the biodiesel oil preparing process that a kind of energy consumption is low, the biofuel quality product is high to be provided.
The preparation method of biofuel provided by the invention comprises the steps: (1) in the presence of alkaline catalysts, with grease and monohydroxy-alcohol contact reacts, makes greasy transformation efficiency reach 80-95 weight %; (2) from step (1) products therefrom, isolate glycerine phase and lightweight oil phase; (3) in the presence of alkaline catalysts, the lightweight oil phase of step (2) gained is contacted with alkaline catalysts with monohydroxy-alcohol, greasy transformation efficiency is reached more than the 98 weight %; (4) product after the contact of step (3) gained is separated, obtain biofuel and monohydroxy-alcohol, the monohydroxy-alcohol that obtains is recycled.
According to method provided by the invention; (1) through controlling the degree that two step transesterification reactions are carried out; At the by-product glycerin that produce in the separating reaction process suitable opportunity, impel balance to move, thereby increased equilibrium conversion to the direction of positive reaction; Reduce the content of triglyceride level and triglyceride in the product, guaranteed in the biofuel product requirement that can be up to state standards of free glycerine and total glycerol content; (2) get back in the reaction tower through in time the monohydroxy-alcohol in the biofuel product being gasified, kept the vapor liquid equilibrium of catalytic tower.According to preferred implementation of the present invention; The preparation method of biofuel provided by the invention also has following advantage: carry out in catalytic tower through making said transesterification reaction (1); Making that monohydroxy-alcohol gas and grease are reverse contacts; Mass transfer effect is superior to traditional mechanical stirring, thereby has improved greasy conversion rate greatly; (2) in time methyl alcohol in the glycerine is gasified directly to get back in the reaction tower and utilize, reduced energy consumption, and improved the storage and the Transport Safety of glycerine.
Description of drawings
Fig. 1 shows the preparing method's of biofuel provided by the invention process flow sheet.
Embodiment
Among the present invention; Said greasy transformation efficiency is meant that grease (chemical constitution is a triglyceride) and monohydroxy-alcohol reaction conversion are that the greasy amount of biological diesel consumption accounts for total greasy weight percent in the raw material of adding, also is that grease that greasy transformation efficiency (weight %)=1-does not transform fully accounts for total greasy percent by weight in the raw material of adding.Can be through not transforming grease (comprising triglyceride, two sweet ester and mono-glyceridess) in vapor-phase chromatography measuring process (1) and step (3) products therefrom fully thus content calculate greasy transformation efficiency.
By method provided by the invention; Greasy transformation efficiency reaches 80-95 weight % in the controlled step (1) effectively; Can guarantee that greasy transformation efficiency reaches more than the 98 weight % in the step (3); Guarantee that the biofuel yield that later separation obtains is high, free glycerine and the total glycerol content requirement that can be up to state standards in the product.
Transesterification reaction of the present invention is preferably carried out in catalytic tower.Said catalytic tower can be conventional various tray columns, is preferably sieve-tray tower.Under the preferable case, said catalytic tower comprises epimere and hypomere, and between upper and lower two sections the hydrops case is set, and upper and lower two sections have a plurality of column plates separately, and column plate has a plurality of sieve apertures, and each column plate has overflow weir.The aperture of each sieve aperture is the 3-8 millimeter, and the total area of the sieve aperture on each column plate is preferably 0.01-0.2 with the ratio of column plate working area.The height of weir of said overflow weir is preferably the 10-100 millimeter, and plate is apart from being preferably 0.2-0.6 rice.The described transesterification reaction of step (1) is carried out at the epimere of catalytic tower, and the described transesterification reaction of step (3) is carried out at the hypomere of catalytic tower.The epimere of said catalytic tower can be 1-5 with the ratio of the theoretical plate number of the hypomere of catalytic tower: 1, be preferably 2-4: and 1, and the premier of said catalytic tower opinion stage number can be the 10-80 piece, is preferably the 15-50 piece, further is preferably the 15-30 piece.
The preparation method of biofuel provided by the invention does not limit the condition of the middle transesterification reaction of step (1) is special, as long as greasy transformation efficiency reaches 80-95 weight % in the ability performing step (1).Preferred monohydroxy-alcohol and greasy mol ratio are 3-20: 1, further be preferably 5-15: and 1, the consumption of said alkaline catalysts is greasy 0.1-2 weight %, is preferably 0.3-1.5 weight %; Catalytic temperature is 50-100 ℃, and being preferably 65-90 ℃ can be 10-60 minute in the catalytic time, and obtaining greasy transformation efficiency fast under preferred 15-30 minute the situation is 80-95 weight %.Therefore, the preferred above-mentioned reaction conditions of the present invention.
Material comprises that grease, catalyzer and monohydroxy-alcohol can be pre-mixed or independently joins the epimere of catalytic tower separately.Before joining catalytic tower, preferably with preheater with they preheatings, the temperature of preheater can be 50-100 ℃, is preferably 65-90 ℃.
According to the preparation method of biofuel provided by the invention, wherein, in the step (2); With step (1) products therefrom isolate glycerine mutually and the method for lightweight oil phase preferably include and from the hydrops case of said catalytic tower, extract step (1) products therefrom out; And send into and carry out settlement separately in the slurry tank, said settled condition comprises that settled temperature for being preferably 40-90 ℃, further is preferably 45-80 ℃; The settled time is preferably 10-60 minute, further is preferably 15-40 minute.Content through glycerine in the lightweight oil phase after the sedimentation is lower than 1.5 weight % under these conditions, particularly under optimum condition, is lower than 0.5 weight %.Can effectively prevent the generation of various side reactions like this, thereby further improve the quality of biofuel product.Said slurry tank can be one or more, can further improve grease and monohydroxy-alcohol transesterification reaction degree through using a plurality of slurry tanks.Said lightweight oil phase is meant that density is light mutually and be positioned at the material on glycerine phase top than glycerine, generally contains mono-glycerides, two sweet esters, triglyceride, biofuel, unreacted monohydroxy-alcohol and alkaline catalysts.
Because a part even most of catalyzer are all taken away by glycerine during separation of glycerin; Thereby the content that causes turning back to catalyzer in the oil phase of hypomere of catalytic tower reduces; Therefore; Method provided by the invention comprises the step of replenishing a spot of catalyzer through to the hypomere of catalytic tower, thereby guarantees the required catalyzer of hypomere reaction.Under the preferable case, among the present invention, in the step (3), the lightweight oil phase of step (2) gained and monohydroxy-alcohol and alkaline catalysts are sent into the catalytic tower from the hypomere top of said catalytic tower.
The condition that the preparation method of biofuel provided by the invention contacts step (3) does not have special the qualification, as long as greasy transformation efficiency reaches more than the 98 weight % in the ability performing step (3).For example, in the step (3) temperature of contact and catalyst levels can with step (1) in identical or different.Under the preferable case, the weight ratio of monohydroxy-alcohol and lightweight oil phase is 1: 5-20 is preferably 1: 8-15; The temperature of contact is 50-90 ℃, is preferably 65-80 ℃; The time of contact is 2-40 minute, is preferably 8-15 minute; The consumption of alkaline catalysts is the 30-90 weight % of base catalysis dosage in the step (1), is preferably 40-80 weight %.
Preparing method according to biofuel provided by the invention; In the step (4), be flash method with the isolating method of product of step (3) gained, the product that is about to step (3) gained carries out flash distillation; The temperature of flash distillation is preferably 120-160 ℃; Further be preferably 130-150 ℃, the time is preferably 5-30 minute, further is preferably 5-20 minute.Can realize so fast the monohydroxy-alcohol in the biofuel being returned in the catalytic tower with gas form, for catalytic tower provides enough monohydroxy-alcohol steam.Said monohydroxy-alcohol steam preferably gets into the catalytic tower from the hypomere bottom of catalytic tower, thereby realizes counter current contact, obtains excellent mass transfer effect.
According to the preparation method of biofuel provided by the invention, wherein, under the preferable case, this method also comprises separating removes step (2) and separates the glycerine that the obtains monohydroxy-alcohol in mutually, and the monohydroxy-alcohol gas that separation obtains sent in the catalytic tower recycles.Said isolating method can be a flash method, and the temperature of flash distillation can be 120-160 ℃.After the flash distillation in the glycerine content of monohydroxy-alcohol be no more than 5 weight %, be generally 0.5-2 weight %.
According to method provided by the invention, the glycerine that flashes off behind the monohydroxy-alcohol gas gets into refining system.Said refining system can be a mature technology well known in the art, and the present invention repeats no more at this.
According to method provided by the invention, wherein, this method comprises that also a part of monohydroxy-alcohol that the catalyzed reaction cat head is refluxed is back to the epimere of catalytic tower, and another part is back to the hypomere of catalytic tower.The ratio of amount of amount and the monohydroxy-alcohol that is back to the catalytic tower hypomere that is back to the monohydroxy-alcohol of catalytic tower epimere can be 1: 1-5.
Among the present invention, said grease can be one or more in various animal oil and the vegetables oil.Said animal oil can be one or more in lard, butter, the sheep wet goods.Said vegetables oil for example can be selected from one or more in VT 18, Oleum Gossypii semen, rapeseed oil, plam oil, peanut oil, sunflower oil and the Semen Maydis oil.
Said alkaline catalysts can be one or more of sodium hydroxide, Pottasium Hydroxide, sodium methylate and potassium methylate.
Said monohydroxy-alcohol can be the aliphatic monobasic alcohol of 1-4 for carbonatoms, for example can be in methyl alcohol, ethanol, propyl alcohol, Virahol, the butanols one or more, is preferably methyl alcohol.
A preferred embodiment of the invention, the preparation method of biofuel provided by the invention can carry out in device as shown in Figure 1.As shown in Figure 1, this device comprises reaction member, separating unit and heating unit, wherein; Said reaction member comprises catalytic tower 1, and said catalytic tower comprises upper and lower two sections 1a, 1b; And upper and lower two sections 1a; Have the hydrops case between the 1b, the epimere 1a of said catalytic tower has the first opening for feed a at the top, has first discharging port A in the bottom; The hypomere 1b of said distillation tower has the second opening for feed b, the 6th opening for feed f and the 8th opening for feed h at the top, the bottom has the second discharge port B and the 3rd opening for feed c; Said separating unit comprises first separator 2, second separator 3 and the 3rd separator 4; Said first separator 2 has an opening for feed, two discharge ports 221,222; The opening for feed of first separator 2 is communicated with the first outlet A of catalytic tower epimere; Two discharge ports 221 and 222 are communicated with the opening for feed of following primary heater 6 with the 6th opening for feed f connected sum of catalytic tower hypomere 1b respectively; Said second separator 3 has an opening for feed 31, two discharge ports 321,322; The opening for feed 31 of second separator 3 is communicated with the discharge port of primary heater 6, and two discharge ports 321,322 are communicated with raw glycerine refining system (not shown) with the second opening for feed b connected sum of catalytic tower hypomere 1b respectively, and said the 3rd separator 5 comprises two sections 5a and 5b; And have an opening for feed e, two discharge port F, a G; The opening for feed e of the 3rd separator 5 is communicated with the second discharge port B of catalytic tower hypomere 1b through following secondary heater 4, and discharge port F is communicated with the 3rd opening for feed c of catalytic tower hypomere 1b, and discharge port G then is used to discharge the coarse biodiesel product.Device shown in Figure 1 also comprises condensing surface 9; Said condensing surface 9 is used for the monohydroxy-alcohol vapor condensation from catalytic tower 1 top exit H effusion; And send into the epimere 1a and/or the hypomere 1b of catalytic tower 1 again, with the utilization ratio of further raising monohydroxy-alcohol steam.The monohydroxy-alcohol of overhead condensation can all be back in the catalytic tower from cat head, also can be divided into one or several bursts of any column plate positions that are back to reactor drum.
The raw material that contains grease and monohydroxy-alcohol and catalyzer at first gets into the epimere 1a of catalytic tower 1 from the first opening for feed a of the epimere 1a of catalytic tower 1; Grease is under the stirring action that the monohydroxy-alcohol steam from the hypomere 1b of catalytic tower 1 rises; Through after the epimere 1a of catalytic tower 1 transesterification reaction, the gained mixture mainly contains fatty ester, glycerine, triglyceride, monoglyceride and unconverted triglyceride level, monohydroxy-alcohol and the catalyzer that transesterify generates.This mixture is discharged from first discharging port A of the bottom of the epimere 1a that is positioned at catalytic tower 1; Get in first separator 2 (like subsider) and carry out phase-splitting; The upper strata component is proceeded transesterification reaction through the hypomere 1b that the 6th opening for feed f loops back catalytic tower 1; Lower floor is the glycerine phase; Glycerine is getting into second separator 3 through opening for feed 31 under the effect of recycle pump 7 after primary heater 6 heating; To be monohydroxy-alcohol proceed reaction from the hypomere 1b that the discharge port 321 at second separator, 3 tops is discharged and the second opening for feed b of hypomere 1b through catalytic tower 1 enters into catalytic tower 1 to low boiling component wherein, and remaining high boiling point liquid phase component (glycerine) is then discharged through the discharge port 322 of second separator, 3 bottoms, is sent to the purification of glycerin system or collects.Returning upper strata component and the monohydroxy-alcohol of the hypomere 1b of catalytic tower 1 discharges through the second discharge port B from the bottom of the hypomere 1b of catalytic tower 1 after the hypomere 1b of catalytic tower 1 proceeds transesterification reaction; After secondary heater 4 (like flashing tower) heating, getting into the 3rd separator 5 under the effect of recycle pump 8 through opening for feed e; Low boiling component wherein is that monohydroxy-alcohol is gasificated into the 3rd opening for feed c that the discharge port F of gas through the top of the 3rd separator 5 returns the hypomere 1b of catalytic tower 1 at epimere 5a; Liquid is cooling realization cooling rapidly then; Thereby further reduce the generation of fatty ester and glycerine reversed reaction; Further reduce the content of monoglyceride, triglyceride and monoglyceride in the product, the quality of product is further improved.Cooled liquid is discharged after washing gets the biofuel product after separating residue monohydroxy-alcohol, glycerine and catalyzer with dehydration from discharge port G as the coarse biodiesel product.
Under the preferable case; When said device also comprises condensing surface 9; Said condensing surface 9 is used for the monohydroxy-alcohol vapor condensation from catalytic tower 1 top exit H effusion, and sends into the epimere 1a and/or the hypomere 1b of catalytic tower 1 again, with the utilization ratio of further raising monohydroxy-alcohol steam.
Following embodiment will specify the present invention.
Embodiment 1
This embodiment is used to explain the preparation method of biofuel provided by the invention.
Used catalytic tower is that total useful volume is that 150 liters, stage number are 80 sieve-tray tower; Count from cat head; Has the hydrops case between the 60th block of column plate of tower and the 61st block of column plate; Each column plate all has overflow weir, and the aperture of the sieve aperture of hydrops case and column plate is the 3-4 millimeter, and the total area of the sieve aperture on each column plate is 0.1 with the ratio of column plate working area.The height of weir of said overflow weir is 20 millimeters, and the plate distance is 0.2 meter.
As shown in Figure 1; To contain the methanol solution of 2.69 weight %KOH and rapeseed oil that acid number is 0.2mgKOH/g with the mol ratio of methyl alcohol and rapeseed oil be 6: 1, the consumption of alkaline catalysts be the ratio of greasy 0.44 weight % be provided to continuously be preheating to 75 ℃ in the preheater after, add by catalytic tower 1 top in the epimere 1a of catalytic tower.Reaction mass (is counted from cat head at the tower epimere 1a of reaction tower; 1-60 piece column plate) in 70-75 ℃ of reaction extraction after 30 minutes down (this moment, greasy transformation efficiency was 90 weight %); Get into slurry tank 2 70 ℃ of following sedimentation phase-splittings after 20 minutes; The lightweight oil phase is counted the 61st block of column plate from cat head and is returned tower hypomere 1b; Methyl alcohol that replenishes and KOH alkaline catalysts get into tower hypomere 1b with the methanol solution form that contains KOH from count the 61st block of column plate from cat head; The amount of alkaline catalysts is 60 weight % of charging catalyzer (being the catalyzer that step (1) gets into catalytic tower epimere 1a) consumption, get into reaction tower hypomere methyl alcohol with isolate that the weight ratio of gained lightweight oil phase is 1: 8 behind the glycerine, lightweight oil phase, methyl alcohol and KOH continue reaction 10 minutes (this moment, greasy transformation efficiency was 98.5 weight %) down at 72-75 ℃; Get into flash distillation methyl alcohol in first separator 3 after glycerine is heated to 125 ℃ by well heater 5, methanol steam is from returning catalytic tower 1 apart from the 59th block of column plate of cat head.The methanol steam of overflowing from the catalyzed reaction top of tower is back to the 1st and the 61st block of column plate of catalyzed reaction distillation tower respectively after condensing surface 9 condensations, and the ratio of the quantity of reflux of the two is 1: 2.Get in second separator 4 after being heated to 140 ℃ from the effusive product heater via 6 of reaction tower lower part outlet B and isolate methyl alcohol; Methanol steam is from getting into the vapor source of the bottom of reaction tower hypomere as tower apart from the 78th block of column plate of cat head; Coarse biodiesel is cooled to 60 ℃ in 5 minutes, obtains the liquid phase coarse biodiesel.
Through gas chromatography determination, the content that this liquid phase coarse biodiesel contains triglyceride level, triglyceride, monoglyceride is respectively 0.2 weight %, 0.3 weight % and 0.5 weight %.Coarse biodiesel gets the biofuel product after washing, dehydration, through gas chromatography determination, the purity of fatty acid methyl ester is 98.8 weight % in the product.
Embodiment 2
This embodiment is used to explain the preparation method of biofuel provided by the invention.
Used catalytic tower is that total useful volume is that 80 liters, stage number are 50 sieve-tray tower; Count from cat head; Has the hydrops case between the 30th block of column plate of tower and the 31st block of column plate; Each column plate all has overflow weir, and the aperture of the sieve aperture of hydrops case and column plate is the 3-4 millimeter, and the total area of the sieve aperture on each column plate is 0.1 with the ratio of column plate working area.The height of weir of said overflow weir is 20 millimeters, and the plate distance is 0.1 meter.
As shown in Figure 1; To contain the methanol solution of 3.80 weight %KOH and Oleum Gossypii semen that acid number is 0.15mgKOH/g with the mol ratio of methyl alcohol and Oleum Gossypii semen be 5: 1, the consumption of alkaline catalysts be the ratio of greasy 1 weight % be provided to continuously be preheating to 70 ℃ in the preheater after, add by catalytic tower 1 top in the epimere 1a of catalytic tower.Reaction mass (is counted from cat head at the tower epimere 1a of reaction tower; The 30th block of column plate) in 65-70 ℃ of reaction extraction after 18 minutes down (this moment, greasy transformation efficiency was 80 weight %); Get into slurry tank 2 55 ℃ of following sedimentation phase-splittings after 30 minutes; The lightweight oil phase is counted the 32nd block of column plate from cat head and is returned tower hypomere 1b; Methyl alcohol that replenishes and KOH alkaline catalysts get into tower hypomere 1b with the methanol solution form that contains KOH from count the 31st block of column plate from cat head; The amount of alkaline catalysts is 40 weight % of charging catalyst levels, get into reaction tower hypomere methyl alcohol with isolate that the weight ratio of gained lightweight oil phase is 1: 10 behind the glycerine, lightweight oil phase, methyl alcohol and KOH continue reaction 12 minutes (this moment, greasy transformation efficiency was 98.0 weight %) down at 72-75 ℃; Get into flash distillation methyl alcohol in first separator 3 after glycerine is heated to 105 ℃ by well heater 5, methanol steam is from returning catalytic tower 1 apart from the 29th block of column plate of cat head.The methanol steam of overflowing from the catalyzed reaction top of tower is back to the 1st and the 31st block of column plate of catalyzed reaction distillation tower respectively after condensing surface 9 condensations, and the ratio of the quantity of reflux of the two is 1: 3.Get in second separator 4 after being heated to 160 ℃ from the effusive product heater via 6 of reaction tower lower part outlet B and isolate methyl alcohol; Methanol steam is from getting into the vapor source of the bottom of reaction tower hypomere as tower apart from the 48th block of column plate of cat head; Coarse biodiesel is cooled to 60 ℃ in 5 minutes, obtains the liquid phase coarse biodiesel.
Through gas chromatography determination, the content that this liquid phase coarse biodiesel contains triglyceride level, triglyceride, monoglyceride is respectively 0.5 weight %, 0.1 weight % and 0.4 weight %.Coarse biodiesel gets the biofuel product after washing, dehydration, through gas chromatography determination, the purity of fatty acid methyl ester is 98.3% in the product.
Embodiment 3
This embodiment is used to explain the preparation method of biofuel provided by the invention.
Used catalytic tower is that total useful volume is that 50 liters, stage number are 30 sieve-tray tower; Count from cat head; Has the hydrops case between the 20th block of column plate of tower and the 21st block of column plate; Each column plate all has overflow weir, and the aperture of the sieve aperture of hydrops case and column plate is the 3-4 millimeter, and the total area of the sieve aperture on each column plate is 0.1 with the ratio of column plate working area.The height of weir of said overflow weir is 20 millimeters, and the plate distance is 0.2 meter.
As shown in Figure 1; To contain the methanol solution of 0.69 weight %KOH and VT 18 that acid number is 0.2mgKOH/g with the mol ratio of methyl alcohol and VT 18 be 10: 1, the consumption of alkaline catalysts be the ratio of greasy 1.5 weight % be provided to continuously be preheating to 70 ℃ in the preheater after, add by catalytic tower 1 top in the epimere 1a of catalytic tower.Reaction mass (is counted from cat head at the tower epimere 1a of reaction tower; The 15th block of column plate) in 65-70 ℃ of reaction extraction after 10 minutes down (this moment, greasy transformation efficiency was 85 weight %); Get into slurry tank 2 70 ℃ of following sedimentation phase-splittings after 15 minutes; The lightweight oil phase is counted the 16th block of column plate from cat head and is returned tower hypomere 1b; Methyl alcohol that replenishes and KOH alkaline catalysts get into tower hypomere 1b with the methanol solution form that contains KOH from count the 16th block of column plate from cat head; The amount of alkaline catalysts is 80 weight % of charging catalyst levels, get into reaction tower hypomere methyl alcohol with isolate that the weight ratio of gained lightweight oil phase is 1: 15 behind the glycerine, lightweight oil phase, methyl alcohol and KOH continue reaction 10 minutes (this moment, greasy transformation efficiency was 99.2 weight %) down at 72-75 ℃; Get into flash distillation methyl alcohol in first separator 3 after glycerine is heated to 115 ℃ by well heater 5, methanol steam is from returning catalytic tower 1 apart from the 15th block of column plate of cat head.The methanol steam of overflowing from the catalyzed reaction top of tower is back to the 1st and the 16th block of column plate of catalyzed reaction distillation tower respectively after condensing surface 9 condensations, and the ratio of the quantity of reflux of the two is 1: 5.Get in second separator 4 after being heated to 150 ℃ from the effusive product heater via 6 of reaction tower lower part outlet B and isolate methyl alcohol; Methanol steam is from getting into the vapor source of the bottom of reaction tower hypomere as tower apart from the 28th block of column plate of cat head; Coarse biodiesel is cooled to 60 ℃ in 5 minutes, obtains the liquid phase coarse biodiesel.
Through gas chromatography determination, the content that this liquid phase coarse biodiesel contains triglyceride level, triglyceride, monoglyceride is respectively 0.2 weight %, 0.4 weight % and 0.2 weight %.Coarse biodiesel gets the biofuel product after washing, dehydration, through gas chromatography determination, the purity of fatty acid methyl ester is 99.4 weight % in the product.
Embodiment 4
This embodiment is used to explain the preparation method of biofuel provided by the invention.
Method according to embodiment 3 prepares biofuel, and different is, counts from cat head, has the hydrops case between the 15th block of column plate of tower and the 16th block of column plate, and promptly the stage number of epimere and hypomere is 1: 1.Obtain the liquid phase coarse biodiesel.
Through gas chromatography determination, the content that this liquid phase coarse biodiesel contains triglyceride level, triglyceride, monoglyceride is respectively 0.5 weight %, 0.8 weight % and 1.2 weight %.Coarse biodiesel gets the biofuel product after washing, dehydration, through gas chromatography determination, the purity of fatty acid methyl ester is 98.5 weight % in the product.
Comparative Examples 1
This embodiment is used to explain the preparation method of biofuel provided by the invention.
Method according to embodiment 3 prepares biofuel, and different is that epimere reaction to greasy transformation efficiency is 75 weight %, obtains the liquid phase coarse biodiesel.
Through gas chromatography determination, the content that this liquid phase coarse biodiesel contains triglyceride level, triglyceride, monoglyceride is respectively 2.5 weight %, 2.8 weight % and 3.5 weight %.Coarse biodiesel gets the biofuel product after washing, dehydration, through gas chromatography determination, the purity of fatty acid methyl ester is 90.5 weight % in the product.
Comparative Examples 2
This embodiment is used to explain the preparation method of biofuel provided by the invention.
Method according to embodiment 3 prepares biofuel, and different is that epimere reaction to greasy transformation efficiency is 96 weight %, obtains the liquid phase coarse biodiesel.
Through gas chromatography determination, the content that this liquid phase coarse biodiesel contains triglyceride level, triglyceride, monoglyceride is respectively 2.8 weight %, 3.2 weight % and 3.0 weight %.Coarse biodiesel gets the biofuel product after washing, dehydration, through gas chromatography determination, the purity of fatty acid methyl ester is 92.2 weight % in the product.
Claims (13)
1. the preparation method of a biofuel, this method comprises the steps: (1) in the presence of alkaline catalysts, with grease and monohydroxy-alcohol contact reacts, making greasy transformation efficiency is 80-95 weight %; (2) from step (1) products therefrom, isolate glycerine phase and lightweight oil phase; (3) with the lightweight oil phase of step (2) gained and monohydroxy-alcohol and alkaline catalysts contact reacts again, greasy transformation efficiency is further reached more than the 98 weight %; (4) material of step (3) gained is carried out biofuel and separate with monohydroxy-alcohol, the monohydroxy-alcohol that obtains recycles, the biofuel that obtains after purifying as product.
2. the preparation method of biofuel according to claim 1; Wherein, said contact reacts is carried out in catalytic tower, and this catalytic tower comprises epimere and hypomere; Has the hydrops case between said epimere and the hypomere; Said epimere is 1-5 with the ratio of the stage number of hypomere: 1, and this method comprises (1) in the presence of alkaline catalysts, with grease and the monohydroxy-alcohol epimere contact reacts in said catalytic tower; Making greasy transformation efficiency is 80-95 weight %, and contact reacts gained material gets into said hydrops case; (2) from the hydrops case, isolate glycerine phase and lightweight oil phase in step (1) products therefrom; (3) in the presence of alkaline catalysts, the lightweight oil phase of step (2) gained is contacted with the hypomere of monohydroxy-alcohol in said catalytic tower, the condition of contact reaches more than the 98 weight % greasy transformation efficiency; (4) product after the contact of step (3) gained is separated, obtain biofuel and monohydroxy-alcohol.
3. the preparation method of biofuel according to claim 1 and 2; Wherein, In the step (1), the condition of reaction comprises that said monohydroxy-alcohol and greasy mol ratio are 3-20: 1, and catalytic temperature is 50-100 ℃; The consumption of said alkaline catalysts is greasy 0.1-2 weight %, and the catalytic time is 10-60 minute.
4. the preparation method of biofuel according to claim 3; Wherein, In the step (1), the condition of reaction comprises that said monohydroxy-alcohol and greasy mol ratio are 5-15: 1, and catalytic temperature is 65-90 ℃; The consumption of said alkaline catalysts is greasy 0.3-1.5 weight %, and the catalytic time is 15-30 minute.
5. the preparation method of biofuel according to claim 2; Wherein, In the step (2); With step (1) products therefrom carry out glycerine mutually and the separation method of lightweight oil phase comprise and extract step (1) products therefrom the hydrops case between said catalytic tower epimere and hypomere out, and send into carry out in the slurry tank settlement separate.
6. the preparation method of biofuel according to claim 5, wherein, in the step (2), said settled condition comprises that settled temperature is 40-90 ℃, the settled time is 10-60 minute.
7. the preparation method of biofuel according to claim 6, wherein, in the step (2), said settled condition comprises that settled temperature is 45-80 ℃, the settled time is 15-40 minute.
8. the preparation method of biofuel according to claim 2, wherein, in the step (3), the lightweight oil phase of step (2) gained and monohydroxy-alcohol and alkaline catalysts are sent into the catalytic tower from the hypomere top of said catalytic tower and are reacted.
9. according to the preparation method of claim 1 or 8 described biofuel; Wherein, In the step (3), the weight ratio of monohydroxy-alcohol and lightweight oil phase is 1: 5-20, and the temperature of contact is 50-90 ℃; The time of contact is 2-40 minute, and the consumption of said alkaline catalysts is the 30-90 weight % of base catalysis dosage in the step (1).
10. the preparation method of biofuel according to claim 9; Wherein, In the step (3), the weight ratio of monohydroxy-alcohol and lightweight oil phase is 1: 8-15, and the temperature of contact is 65-80 ℃; The time of contact is 8-15 minute, and the consumption of said alkaline catalysts is the 40-80 weight % of base catalysis dosage in the step (1).
11. the preparation method of biofuel according to claim 1 and 2 wherein, in the step (4), carries out flash distillation with the isolating method of product of step (3) gained for the product with step (3) gained, the temperature of flash distillation is 120-160 ℃.
12. the preparation method of biofuel according to claim 2, wherein, this method also comprises separating removes step (2) and separates the glycerine that the obtains monohydroxy-alcohol in mutually, and the monohydroxy-alcohol that separation obtains sent in the catalytic tower recycles.
13. according to the preparation method of claim 2,5,8 or 12 described biofuel, wherein, said catalytic tower is that stage number is the sieve-tray tower of 10-80 piece.
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| CN1850944A (en) * | 2006-05-22 | 2006-10-25 | 暨南大学 | Method for synthesizing biodiesel |
| CN1865401A (en) * | 2006-06-19 | 2006-11-22 | 菏泽华瑞油脂有限责任公司 | Method for preparing biological diesel oil using high acid value cottonseed oil |
| CN1876764A (en) * | 2006-07-07 | 2006-12-13 | 菏泽华瑞油脂有限责任公司 | Method for synthesizing biodiesel-isopropyl fatty acid by waste oil in meat plant |
| WO2007059512A2 (en) * | 2005-11-15 | 2007-05-24 | Domestic Energy Partners, Llc | Transesterification of oil to form biodiesels |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007059512A2 (en) * | 2005-11-15 | 2007-05-24 | Domestic Energy Partners, Llc | Transesterification of oil to form biodiesels |
| CN1850944A (en) * | 2006-05-22 | 2006-10-25 | 暨南大学 | Method for synthesizing biodiesel |
| CN1865401A (en) * | 2006-06-19 | 2006-11-22 | 菏泽华瑞油脂有限责任公司 | Method for preparing biological diesel oil using high acid value cottonseed oil |
| CN1876764A (en) * | 2006-07-07 | 2006-12-13 | 菏泽华瑞油脂有限责任公司 | Method for synthesizing biodiesel-isopropyl fatty acid by waste oil in meat plant |
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