CN101358140A - Synthetic process of bio diesel oil and equipment - Google Patents
Synthetic process of bio diesel oil and equipment Download PDFInfo
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- CN101358140A CN101358140A CNA2007100184005A CN200710018400A CN101358140A CN 101358140 A CN101358140 A CN 101358140A CN A2007100184005 A CNA2007100184005 A CN A2007100184005A CN 200710018400 A CN200710018400 A CN 200710018400A CN 101358140 A CN101358140 A CN 101358140A
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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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- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The present invention relates to a method for synthesizing biodiesel (namely, fatty acid methyl ester), in particular to a method for synthesizing biodiesel by utilizing materials such as edible oil and fat (namely, hogwash oil) coming from kitchens and crude animal and plant grease. The method at least has the following characteristics: utilizing effective strong electrolyte and water to degum crude oil and remove impurities from the crude grease; utilizing special catalyst to carry out one-step esterification and transesterification reaction; utilizing active carrier to refine biodiesel and crude glycerine; and utilizing carbon dioxide to neutralize reactant mixture. The method has the advantages of simple and easy technique, low cost, no pollutant production, etc. The method for synthesizing the biodiesel includes three processing steps: a small amount of strong electrolyte is added to treat crude animal and plant grease and hogwash oil, and water is then added to hydrate the crude animal and plant grease and the hogwash oil; under the function of the special catalyst, the processed oil and fat is esterified and transesterified with methanol in one step; and the produced biodiesel and glycerine are refined and purified. Afterwards, a qualified product is produced by the processes of precipitation and centrifugalization. The refined crude glycerine is depressurized, distilled, dehydrated and purified, so that high-purity glycerine is produced.
Description
Technical field
The present invention relates to synthesis technique and equipment that a kind of biofuel is a fatty acid methyl ester, particularly about utilizing meal kitchen waste edible oil fat (promptly purchasing oil), crude vegetable oil fat, coarse motion thing grease etc. to be the synthesis technique and the equipment of raw material production biofuel.Belong to biomass energy and resource reutilization field.
Technical background
Non-renewable petroleum resources are made the energy more nervous by exploitation use on a large scale, and seeking the environment-friendly type renewable energy source becomes one of important topic of petrochemical industry and energy field.The inventor is divided into four operational paths with the preparation method of biofuel by the catalyzer difference:
(1) homogeneous catalysis lactide reaction process wherein can be divided into wet method and dry method two classes again, and catalyzer mainly is inorganic acid alkali and organic acids and base;
(2) heterogeneous catalysis lactide reaction process wherein can be divided into solid base catalyst and solid acid catalyst two classes again, and majority is a composition metal ouch mould assembly oxide compound, or its hydrate;
(3) biological enzyme lactide metallization processes;
(4) overcritical on-catalytic lactide metallization processes, etc.
Wherein, at present both at home and abroad the most ripe with the most use be the technology of catalyzer still with the soda acid aqueous solution, but that its shortcoming is a transformation efficiency is lower, and has more process spent water to produce; Its advantage is that catalyzer is inexpensive, technology is simple.
Animal-plant oil is that its main component of fatty acid glycerine fat is: C
16, C
18, C
22, C
24Mixed fatty glycerides, wherein, with C
18Glycerin fatty acid ester is main, generally accounts for 50～80%; Animal grease mainly is that saturated fatty acid is that stearin is main, but also contains part unsaturated fatty acids acid glyceride; Be tripalmitin based on unsaturated fatty acids in the Vegetable oil lipoprotein, but also contain the fractional saturation glycerin fatty acid ester.And no matter be stearin or tripalmitin, wherein mainly be the glyceryl ester of 18 carbon fatty acids; Based on oleic acid (contain one two keys) glyceryl ester, and be stearic acid (not containing two keys) glyceryl ester based on saturated fatty acid in the animal oil in the vegetables oil; In jatropha oil, tea-seed oil, Semen Maydis oil, Oleum Cocois, sesame oil, tung oil, Viscotrol C, coptis wood oil, flax wet goods composition except mainly containing the oleic acid (vaccenic acid-[9]-acid of two keys, Oleic acid) outside the glyceryl ester, also be rich in linolic acid (the 18 carbon diene-[9 of two two keys, 12]-acid, Linoleic acid) glyceryl ester and a certain amount of linolenic acid (18 carbon triolefins-[9 that contain three two keys, 12,15]-and acid, Linolenic acid) glyceryl ester.They are not only the raw material of preparation reducing blood-fat Altace Ramipril in the pharmacy industry, and be the best raw material of preparation biofuel, by their the preparation its good fluidity of biofuel, condensation point is low, cold filter clogging temperature is low, and the cetane value that characterizes diesel engine anti-knocking property index is better than petroleum diesel all more than 50.
Summary of the invention
The present invention includes biofuel synthetic three partial contents: the pretreatment process and the technology of (1) stock oil; (2) one-step catalytic esterification-lactide method and technology; (3) the refining and purifying technique of biofuel and glycerine.And required major equipment and device etc. are produced in the serialization of above-mentioned three processes.
1. stock oil pretreatment technology
Generally all contain a certain amount of peptized impurities in the crude oil, as phlegmatic temperament, phosphatide, protein, triglyceride, trickle food (in the kitchen waste edible oil of especially eating) or the like, they will reduce esterification and lactide reaction efficiency, reduce quality product and yield.The present invention adopts and adds strong electrolyte and add the technology that water hydratable comes unstuck and purifies, and can purify crude oil effectively, is follow-up esterification and lactide prepared in reaction fatty acid methyl ester, and promptly biofuel lays the first stone.Its technology is simple, the easy row, with low cost of low-temperature atmosphere-pressure, operation.
A kind of treatment process that is used for the coarse raw materials crude oil of production of biodiesel, be characterized in special pretreatment reaction still, the thick grease of raw material is normal pressure, 50～80 ℃ and fully under the agitation condition, add strong electrolyte and add water hydratable, described strong electrolyte available period table pentels, the promptly corresponding acid of the hydrate of nitrogen, phosphorus, arsenic, antimony, bismuth oxide compound, wherein best with the phosphoric acid effect.The using method of described strong electrolyte phosphoric acid is divided two kinds: at 50～80 ℃, and under fully stirring, a kind of is to add trace or i.e. 0.01～6.0% (m/m) on a small quantity, and high density i.e. 75～85% (m/m) phosphoric acid.Second kind is to add i.e. 20～50% (m/m) of volume, lower concentration i.e. 30～45% (m/m) phosphoric acid, with the peptized impurities in the thick grease of raw material, as phlegmatic temperament, organic phospholipid, protein, triglyceride, trickle food (in the non-oil in kind in the kitchen of especially eating) etc., the electric charge physical-chemical reaction takes place, make these peptized impurities bear charge separation of going ahead of the rest, then add 2～10% water and carry out aquation and make it flocculation and assemble, from grease, dissociate out.Adopt then heat sinkly fall, centrifuging process is removed, and can obtain comparatively ideal purification stock oil.
Resulting peptized impurities gel is generally transparent or semitransparent light yellow or orange or sorrel liquid, wherein contains a considerable amount of Yelkin TTS, if turnout can extract it greatly, also has higher economic value.
2. single stage method esterification technique
By the fatty acid glycerine fat that above-mentioned prepared purification stock oil also promptly purifies, removed the various impurity of most peptizations, this is very necessary for follow-up biodiesel manufacture reaction.But still containing a certain amount of free fatty acids, reaction has disadvantageous effect to lactide for they.General preparation biodiesel processes all needs they are separated in advance, and the lactide reaction is carried out smoothly.Especially higher to free fatty acid content is the higher raw oil material of acid number, particularly important as meal kitchen trench wet goods.And this part free fatty acids also is the raw material of biofuel.
A kind of characteristics that prepare biodiesel technology are: adopt single stage method esterification-lactide metallization processes biodiesel synthesis, its characteristics are as follows: the raw oil material behind the purifying is added under atmospheric pressure at room in the reactor, start and stir; With 4～8 times of methyl alcohol, add at normal temperatures in the raw oil material again, fully stir, make immiscible oleyl alcohol two-phase thorough mixing to raw oil material equivalent (equivalent of glycerin fatty acid ester and free fatty acids sum is as the criterion with saponification value calculating); Add under the reflux temperature in 1～3% the special-purpose catalyst reaction mixture under stirring being lower than then; Carry out esterification-lactide reaction of 1～4 hour, make free fatty acids and fatty acid glycerine fat in the refining grease, carry out esterification and lactide reaction simultaneously, i.e. obtain fatty acid methyl esters, i.e. biofuel; Separating methanol then after confirming methyl alcohol oneself having taken off, adds atlapulgite again and makes with extra care decolouring.And be blown into carbonic acid gas from the bottom simultaneously, in and basic catalyst.This moment, coarse biodiesel and raw glycerine all can be made with extra care.Obviously, one-step technology has saved the alkali-refining deacidification or the pre-esterification deacidification of free lipid acid in the raw oil material, and the isolating two procedures of product, and whole synthesis technique is greatly simplified, and has saved facility investment and process cost.And the product yield of biofuel also increases, and quality product reaches GB diesel oil GB252 and German biofuel DIN-RME standard.
Described special-purpose catalyst comprises mineral alkali, organic bases, the compound alkali of bimetal.Be mainly the oxyhydroxide and the alkali-metal rudimentary alcoholate of basic metal or alkaline-earth metal, and close composite solid alkalimetal oxide Mg by the magnalium ouch of hydrotalcite preparation
2Three class catalyzer such as Al.
3. serialization production equipment and major equipment
A kind of serialization production equipment of biofuel is characterized in comprising three workshop sections:
(1) first workshop section, the pre-treatment workshop section of raw oil material
Its technology is, adopts special ionogen to add water hydratable technology as broken coagulating/flocculation agent and employing, under the low-temperature atmosphere-pressure condition the various colloid impurity that are harmful to the biofuel building-up reactions removed.
The major equipment of this workshop section has: be provided with the outer electric heater unit (available far-infrared heating device) of steam heating coil or still, raw oil material jar, inter settling tank, supercentrifuge or horizontal or vertical blade formula or disk type filter, refining raw oil material jar, peptized impurities storage tank etc. in the stock oil pretreatment reaction still that band stirs, the described reactor.And supporting required hydro-thermal boiler or electric heating device, pump, electrical instrumentation, pipeline valve etc.;
(2) second workshop sections, esterification/lactide reaction workshop section
Its technology is, esterification in advance of pretreated refining raw oil material or alkali refining are removed free fatty acids, and directly enter reactor, stir to add excessive normal methyl alcohol down, with a spot of esterification/lactide catalyzer, carry out esterification/lactide single stage method reaction simultaneously.Be reflected under the reflux temperature of normal pressure and methyl alcohol and carry out.Along with methyl alcohol constantly with free fatty acids and triglyceride generation esterification/lactide reaction, methyl alcohol constantly is consumed, reflux temperature will raise to some extent, finishes until esterification/lactide reaction; Then, with the still separating methanol, will pay special attention to this moment, prevents that temperature from rising suddenly.Temperature can not surpass 80, and is the highest 90 ℃; Then,, add 1～5% atlapulgite, under agitation make with extra care decolouring with the reinforced method of sealing chamber.Enter the product mixture slurry tank after finishing.
The major equipment of this workshop section has: esterification/lactide stirred autoclave, the described reactor that band stirs is provided with in methanol eddy device and separating methanol device, sealing chamber feeding device, methyl alcohol test tank, the described reactor and is provided with steam heating coil or electric heater unit, fresh methanol jar, reclaims methyl alcohol tundish, substandard product freshening jar etc.And supporting required hydro-thermal boiler or electric heating device, pump, electrical instrumentation, pipeline valve etc.;
(3) the 3rd workshop sections, product purification and separation and glycerine subtract the steaming recycle section
Its technology is, after esterification and separating methanol were finished, the esterification reaction mixture and the raw glycerine that generate in the reaction kettle of the esterification added atlapulgite and decolour assorted refiningly, and through 1～2 hour, after refining the finishing, descending flowed into the product mixture slurry tank.Slurry tank wherein contains fatty acid methyl ester (biofuel), raw glycerine, has adsorbed the reaction mixtures such as carclazyte of dark reaction by product and colloid etc., suitably most adsorptive clays are discharged at the bottom of still after the sedimentation, extract mixed solution out from the middle and lower part of jar, pump into supercentrifuge, perhaps 30 ℃ of left and right sides long period sedimentations, biofuel (relative density is 0.85～0.91) and raw glycerine (relative density is 1.2613) are separated, obtain qualified product, send into the finished product jar.Raw glycerine is sent into the raw glycerine tundish, and then delivers to vacuum distillation apparatus, reclaims the high purity refining glycerine.
The major equipment of this workshop section has: esterification reaction mixture solid-liquid separation jar (at least two), esterification mixed solution slurry tank (at least two), whizzer (two), biofuel finished product jar (at least two), substandard product freshening jar, still kettle, the far-infrared heating device of described still kettle, or heat carrier furnace, they can satisfy the requirement of the highest 250 ℃ of temperature, described still kettle is provided with rectifying tower, described rectifying tower has 10～12 theoretical stages, described rectifying tower cat head is provided with fractional distillating tube (thermal backflow is provided) and cold reflux inlet, the overhead condensation water cooler, knockout drum, vacuum pump (as liquid-ring vacuum pump), described vacuum pump can satisfy and is not less than the 700mmHg vacuum requirements, high purity glycerine finished product jar, defective glycerine freshening jar, residual jar of still, etc.
Technical process
The present invention prepares the technical process of biofuel shown in Figure of description, is summarized as follows:
Earlier the thick grease of coarse motion plant is carried out pre-treatment, in the reactor that has stirring, heating and temperature measuring equipment, add strong electrolyte then, fully stir, and slowly heating.At this moment, reaction mixture is a dark-brown.Treat that temperature rises to 60 ℃, add water purification, fully stir, carry out aquation.Then, keep and carry out the hydration reaction removal of impurities of coming unstuck under 60 ± 2 ℃.After finishing, mixture of reaction products carries out centrifugation, obtains clarifying the refining grease of yellow transparent.And obtain translucent gluey sediment liquid, fuel oil be can make or Yelkin TTS, sterol etc. extracted; The refining grease that will obtain then adds another stirred autoclave that has evaporator overhead condenser and backflow dealcoholysis device.Stir adding anhydrous methanol down, and then add catalyzer, slowly heating under ceaselessly stirring is to backflow.Reflux after half an hour, reactant yellow mud pulpous state disappears, and becomes transparent, orange gradually.Continue to reflux and be tending towards finishing instead until esterification and lactide reaction.Separating methanol then adds atlapulgite after deviating from methyl alcohol, stirs refining.Be blown into carbonic acid gas from the bottom simultaneously, in and basic catalyst.Settlement separate then, reaction product promptly is divided into three layers after half an hour.The lowest layer is the brown carclazyte, and the centre is the raw glycerine layer, and the upper strata is biofuel, and the three is very easy separately.The upper strata bio-diesel layer promptly gets biofuel at last through the separation of separating centrifuge again; The raw glycerine layer passes through underpressure distillation again, just can obtain high purity glycerine.
Process characteristic
The process characteristic for preparing biofuel according to foregoing invention content and technical process the present invention is as follows:
(1) utilize effective strong electrolyte to the raw oil material removal of impurities of coming unstuck: to utilize the periodictable pentels, the promptly corresponding acid of the hydrate of nitrogen, phosphorus, arsenic, antimony, bismuth oxide compound is as strong electrolyte, to the come unstuck pre-treatment of removal of impurities of thick glyceride stock, having improved greasy esterification and lactide generation fatty acid methyl ester is the yield and the quality of biofuel.
(2) utilize the esterification of special catalyst single stage method: utilize special catalyst can make free lipid acid and triglyceride while or esterification successively and lactideization in the raw oil material, it is biofuel that a step is converted into fatty acid methyl ester.This has just saved usually the processing step of separation of free fatty acids from raw oil material in advance, carries out esterification then in another reactor separately.Otherwise free fatty acids can hinder the lactide process of triglyceride.This has just saved the two procedures of from raw oil material separation of free fatty acids and esterification thereof.This special catalyst is the oxyhydroxide or the complex oxide of special mineral alkali, organic bases and second family three-group metal element.This one-step technology is higher to those free fatty acid contents especially to be the high raw oil material of acid number, more suitable as the animal-plant oil that sewer oil, free fatty acid content are higher.
(3) active carrier refining biodiesel and raw glycerine: make product reach biofuel and ordinary diesel oil standard-required.
(4) carbonic acid gas neutralization reaction mixture: utilize carbonic acid gas to finished in the reaction mixture catalytic esterification and lactide reaction basic catalyst carry out neutralizing treatment, simple for process, expense is low, contamination-free produces.
Inventive embodiments
The embodiment of the invention is as follows:
The pre-treatment of [routine 1-1] thick rapeseed oil is in the reactor that has stirring and temperature measuring equipment, the thick rapeseed oil that adds the color depth (yellowish red color) of 545.9 parts of weights earlier, add concentration then and be 0.546 part of weight (0.10%) of phosphoric acid (relative density about 1.69) of 85%, fully stir, and slowly heating.At this moment, reaction mixture is a dark-brown.Rise to 60 ℃ in about 0.5 hour, and kept under 60 ± 2 ℃, add 16.5 parts heavy water purification (3.02%), fully stir, carry out aquation.After water added about 3 minutes, the reaction mixture color immediately shoaled, and was yellow.Then, keep the removal of impurities hydration reaction that comes unstuck that carried out under 60 ± 2 ℃ 38 minutes.Then, mixture of reaction products carries out centrifugation, condition 5000rpm * 15min.Obtain clarifying 524.1 parts of weights of yellow transparent sirasimeyu, yield is 96.01%.
The pre-treatment of [routine 1-2] thick rapeseed oil in the reactor that has stirring and temperature measuring equipment, adds the thick rapeseed oil of the color depth (light coffee color) of 261.1 parts of weights with routine 1-1 earlier, fully stirs, and slowly heats.Rose to 60 ℃ in about 0.5 hour, and kept under 60 ± 2 ℃, add concentration then and be 0.16 part of weight (0.06%) of phosphoric acid (relative density about 1.69) of 85%, at this moment, reaction mixture is a dark-brown.Fully stir after 15 minutes, 64 ℃ add 8.0 parts heavy water purification (3.06%) down, fully stir, and carry out aquation.After water added about 3 minutes, the reaction mixture color immediately shoaled, and is milk yellow.Then, keep the removal of impurities hydration reaction that comes unstuck that carried out under 60 ± 2 ℃ 20 minutes.Then, mixture of reaction products carries out centrifugation, condition 5000rpm * 25min.Obtain clarifying 246.6 parts of weights of yellow transparent sirasimeyu, yield is 94.5%.
The pre-treatment of [routine 1-3] meal kitchen sewer oil in the reactor that has stirring and temperature measuring equipment, adds the sewer oil (its relative density is about 0.8233) of the yellow dulling of 123.5 parts of weights with routine 1-1 earlier, fully stirs, and slowly heats.Rose to 60 ℃ in about 0.5 hour, and kept under 60 ± 2 ℃, add concentration then and be 0.15 part of weight (0.12%) of phosphoric acid (relative density about 1.69) of 85%, at this moment, reaction mixture deepens.Fully stir after 30 minutes, 64 ℃ add 10.0 parts heavy water purification (8.09%) down, fully stir, and carry out aquation.After water added about 3 minutes, the reaction mixture color immediately shoaled, and was shallow milk yellow.Then, keep the removal of impurities hydration reaction that comes unstuck that carried out under 60 ± 2 ℃ 20 minutes.Then, at one night of mixture of reaction products sedimentation, water acid layer appears in container bottom, is easy to flow out from Bottoming, accounts for 11.23% of 133.5 parts of total materials after weighing.Then upper liquid is carried out centrifugation, condition 3500rpm * 25min.The centrifugal dregs solids that is white in color obtains clarifying the refining 108 parts of weights of sewer oil of yellow transparent, and yield is 87.5%.
The pre-treatment of [routine 1-4] meal kitchen sewer oil in the reactor that has stirring and temperature measuring equipment, adds the sewer oil (its relative density is about 0.8233) of the yellow dulling of 191.5 parts of weights with routine 1-3 earlier, fully stirs, and slowly heats.Rose to 60 ℃ in about 0.5 hour, and kept under 60 ± 2 ℃, add concentration then and be 1.92 parts of weights (1.0%) of phosphoric acid (relative density about 1.69) of 85%, at this moment, reaction mixture deepens.Fully stir after 30 minutes, 64 ℃ add 10.0 parts heavy water purification (5.22%) down, fully stir, and carry out aquation.After water added about 3 minutes, the reaction mixture color immediately shoaled, and was shallow milk yellow.Then, keep the removal of impurities hydration reaction that comes unstuck that carried out under 60 ± 2 ℃ 20 minutes.Then, at one night of mixture of reaction products sedimentation, water acid layer appears in container bottom, is easy to flow out from Bottoming, accounts for 7.44% of 201.5 parts of total materials after weighing.Then upper liquid is carried out centrifugation, condition 3500rpm * 25min.The centrifugal dregs solids that is white in color obtains clarifying the refining 169.6 parts of weights of sewer oil of yellow transparent, and yield is 88.6%.
One of sewer oil system biofuel has the stirred autoclave of evaporator overhead condenser and backflow dealcoholysis device after [routine 2-1] removal of impurities of coming unstuck, and its still is outside equipped with electric feeder apparatus.At first, heavily handle back sewer oil (100.0%) with 104.0 parts and add at normal temperatures and pressures in the stirring tank, this sewer oil is the product of [routine 1-3].Stir the anhydrous methanol that adds 27.5 parts of weights (21.0%) down and add in the reactor, and then add 1# 1.56 parts of weights of basic catalyst (1.5%), described 1# catalyzer is the oxyhydroxide of basic metal or alkaline-earth metal.Slowly heating only has a small amount of backflow during to 65 ℃ under ceaselessly stirring, and reaction mixture is the yellow mud pulpous state.Just reflux in a large number until 90～100 ℃.Reflux after half an hour, reactant yellow mud pulpous state disappears, and becomes transparent, orange gradually.After the back flow reaction 75 minutes, esterification and lactide reaction are tending towards finishing, and reaction product is the transparent oily of orange.Separating methanol is then deviate from 11.5 parts of weights of methyl alcohol (be about add methyl alcohol 42%).The atlapulgite that adds 2.01 parts of weights (2.0%) then stirred refining 1 hour under 80～90 ℃.Be blown into carbonic acid gas from the bottom simultaneously, in and basic catalyst.Reaction product promptly is divided into three layers after half an hour.The lowest layer is the brown carclazyte, be yellow glycerin layer up, and the upper strata is biofuel, is yellow to light yellow, but dulling is arranged slightly.After sedimentation is spent the night again, become substantially transparent, the three is very easy separately.Through the last 96.3 parts of weights of qualified biofuel that get complete clear of the separation of separating centrifuge, yield is 92.6% to the upper strata biofuel again.
One of sewer oil system biofuel has the stirred autoclave of evaporator overhead condenser and backflow dealcoholysis device after [routine 2-2] removal of impurities of coming unstuck, and its still is outside equipped with electric feeder apparatus.At first, heavily handle back sewer oil (100.0%) with 218.9 parts and add at normal temperatures and pressures in the stirring tank, this sewer oil is the product of [routine 1-4].Stir the anhydrous methanol that adds 65.67 parts of weights (30.0%) down and add in the reactor, and then add 2# 3.28 parts of weights of basic catalyst (1.5%), described 2# catalyzer is alkali-metal alcoholate compound, and described alcohol is lower alcohol.Slowly heating only has a small amount of backflow during to 80 ℃ under ceaselessly stirring., reaction mixture is the yellow mud pulpous state and just refluxes in a large number until 90～100 ℃.Reflux after 45 minutes, reactant becomes transparent, orange gradually, and the yellow mud pulpous state disappears.After the back flow reaction 80 minutes, esterification and lactide reaction are tending towards finishing, and reaction product is the transparent oily of orange.Separating methanol is then deviate from 43.5 parts of weights of methyl alcohol (be about add methyl alcohol 2/3rds).The atlapulgite that adds 4.5 parts of weights (2.06%) then stirred refining 1 hour under 80～90 ℃.Be blown into carbonic acid gas from the bottom simultaneously, in and basic catalyst.Reaction product promptly is divided into three layers after half an hour.The lowest layer is the brown carclazyte, be yellow glycerin layer up, and the upper strata is biofuel, is yellow to light yellow, but dulling is arranged slightly.After sedimentation is spent the night again, become substantially transparent, the three is very easy separately.Through the last 206.8 parts of weights of qualified biofuel that get complete clear of the separation of separating centrifuge, yield is 94.5% to the upper strata biofuel again.
Thick one of rapeseed oil system biofuel has the stirred autoclave of evaporator overhead condenser and backflow dealcoholysis device after [routine 2-3] pre-treatment, and its still is outside equipped with electric feeder apparatus.At first, 150.0 portions of heavy muddy slightly rapeseed oils of tawny (100.0%) are added in the stirring tank at normal temperatures and pressures.Then, under agitation the anhydrous methanol with 31.5 parts of weights (21.0%) adds in the reactor, and then adds 1# 1.5 parts of weights of basic catalyst (1.0%).Slowly heating under ceaselessly stirring, 80 ℃ to the reactor bottom, and begin to reflux during 65 ℃ of reflux temperatures.Reflux after 1 hour, reaction mixture deepens slightly.After the back flow reaction 5 hours, esterification and lactide reaction are tending towards finishing, and reaction product is the transparent oily of orange.Separating methanol is then deviate from 11.9 parts of weights of methyl alcohol (be about add methyl alcohol 37.8%).Be blown into carbonic acid gas from the bottom then, in and basic catalyst.The decolouring flocculating aids that adds 10.0 parts of weights (6.67%) then, filtered while hot.Reaction product promptly is divided into two-layer after half an hour.Lower floor is the brown raw glycerine, and the upper strata is biofuel, is yellow, gets 167.9 parts of weights, yield 119.3%.If the upper strata biofuel weighs through the last qualified biofuel part that gets complete clear of the separation of separating centrifuge again, yield is 113.3%.
Thick one of rapeseed oil system biofuel has the stirred autoclave of evaporator overhead condenser and backflow dealcoholysis device after [routine 2-4] pre-treatment, and its still is outside equipped with electric feeder apparatus.At first, 150.0 portions of heavy muddy slightly rapeseed oils of tawny (100.0%) are added in the stirring tank at normal temperatures and pressures.Then, under agitation the anhydrous methanol with 31.5 parts of weights (21.0%) adds in the reactor, and then adds 1.5 parts of weights of 3# basic catalyst (1.0%), and described 3# catalyzer is severe alkali-metal oxyhydroxide.Slowly heating under ceaselessly stirring, 90 ℃ to the reactor bottom, and begin to reflux during 70 ℃ of reflux temperatures.Reflux after 30 minutes, reaction mixture deepens slightly.After the back flow reaction 2 hours 35 minutes, esterification and lactide reaction are tending towards finishing, and reaction product is the transparent oily of orange.Separating methanol is then deviate from 14.3 parts of weights of methyl alcohol (be about add methyl alcohol 45.4%).Reaction product promptly is divided into two-layer after half an hour.Following 1 layer is the brown raw glycerine, and the upper strata is biofuel, is yellow, gets 154.7 parts of weights, yield 103.1%.If the upper strata biofuel weighs through the last qualified biofuel part that gets complete clear of the separation of separating centrifuge again, yield is 97.9%.
One of [routine 2-5] peanut oil system biofuel has the stirred autoclave of evaporator overhead condenser and backflow dealcoholysis device, and its still is outside equipped with electric feeder apparatus.At first, 100.0 parts of weights (0.109mol) muddy slightly rapeseed oils of tawny (100.0%) are added in the stirring tank at normal temperatures and pressures.Then, under agitation with 21.0 parts of weight (0.656mol of anhydrous methanol, 21.0%) add in the reactor, and then to add the described 4# catalyzer of 2.0 parts of weights of 4# magnalium solid base catalyst (2.0%, Yixing, Jiangsu catalyst plant is produced specially for this problem) is magnalium Mg2Al composite solid alkaline catalysts.Slowly heating under ceaselessly stirring begins to reflux during to 64 ℃ of reflux temperatures.Reflux after 30 minutes, reaction mixture is creamy white.After the back flow reaction 2 hours, esterification and lactide reaction are tending towards finishing, and reaction product is the translucent oily of yolk.Separating methanol is then deviate from 12.0 parts of weights of methyl alcohol (be about add methyl alcohol 57.1%).Reaction product promptly is divided into two-layer after half an hour.Following 1 layer is the brown raw glycerine, and the upper strata is biofuel, is yellow, gets 99.1 parts of weights, yield 99.1%.Become partly to solidify shape, about 26 ℃ of condensation point after being chilled to normal temperature.
The physico-chemical property and the chemical composition analysis of refining raw oil material are as shown in table 1 after [routine 3-1] pre-treatment.
The physico-chemical property of raw oil material and chemical composition analysis after table 1. pre-treatment
Refining crude oil suggestion quality index after [routine 3-2] pre-treatment is as table 2.
Refining crude oil suggestion quality index after table 2. pre-treatment
| Project | Index | Test method |
| Iodine number (IV) | 110-115 | SY2114-82 |
| Saponification value (SV) | 170-191 | SY2604-77 |
| Free fatty acid content [notes] | 0.3％，max. | GB264-83/SY2454-82 |
| Phosphatide | 25Ppm，max | SY2676-82 |
| Water content | 0.1％，max | GB260-77 |
| Impurity | ≯0.03％(m/m) | GB511-77 |
[notes] this to except the sewer oil.
[routine 3-3] German biofuel quality standard is as table 3.
The biofuel quality index, China is drafted, and is referring now to the German biofuel tentative standard DIN-RME control that Europe is assert, as shown in table 3.
The German biofuel quality index of table 3. (German DIN-RME standard)
| NO | Project | Index |
| 1 | Density, (g/cm 3，15℃) | 0.875-0.91 |
| 2 | Flash point in closed cup (P.M), ℃ | 110，min |
| 3 | Kinematic viscosity (mm 2/S，40℃) | 3.5-5.0 |
| 4 | Neutralization value, mg KOH/g | 0.5，max |
| 5 | Free glycerol % (m/m) | 0.02，max |
| 6 | Total glycerol content (after the hydrolysis), % (m/m) | 0.25，max |
| 7 | Carbon residue, full fraction (CCR), % (m/m) | 0.05，nax |
| 8 | Cetane value | 50，min |
| 9 | Sulfur compound, % (m/m) | 0.03，max |
| 10 | Total sulfur, % (m/m) | 0.01，max |
| 11 | Methyl alcohol, % (m/m) | 0.3，max |
| 12 | Iodine number, % (m/m) | 115, max (,, annotating) so value is controlled an editor by half temporarily because of containing a large amount of animal grease to sewer oil |
| 13 | Total impurities, mg/kg (PPM) | 30，max |
| 14 | CFPP when additive-free (), ℃ | -8, max (cold filter clogging temperature-editor annotates) |
| 15 | Water, mg/kg (PPM) | 300，max |
By table 3 data as seen, main indexes is density, cetane value, total sulfur content, cold filter clogging temperature (CFPP), moisture content and foreign matter content etc. in the biofuel quality index, can select key index as controlling index according to the different material oil and the different times condition of production, and other index can obtain to satisfy with being readily solved.Wherein the specific targets of iodine number need to take the circumstances into consideration to adjust according to the size that contains the animal grease amount in the sewer oil in table 3, can press a half value temporarily, i.e. about 80 controls.
[routine 3-4] utilizes the quality examination result of the biofuel of sewer oil preparation, and be as shown in table 4.
Waste edible oil ester (sewer oil) methyl alcohol lactide biofuel quality is pressed GB252-94 standard analysis evaluation temporarily, and the quality examination result of prepared sample is as shown in table 4.
Table 4.Sewer oil biofuel quality examination result
| Density, kg/M 3 | Actual measurement | 0.875～91 | 0.8821 | GB/T 1884 |
| Condensation point, ℃, ≯ | -10 | - | -12 | GB/T 510 |
| Cold filter clogging temperature, ℃, ≯ | -5 | -8 | -6 | SH/T 2413 |
| Flash-point (remaining silent), ℃, ≮ | 65 | 110 | 112 | GB/T261 |
| Kinematic viscosity, mm 2/S，40℃ | 0.5～3.0 | 3.5～5.0 | 4.1 | |
| Neutralization value (acid number), mg KOH/g | - | 0.5，max | 0.5 | GB264- 83/SY2454 -82 |
| Free glycerol % (m/m) | - | 0.02，max | ||
| Total glycerol content (after the hydrolysis) % (m/m) | - | 0.25，max | GC | |
| Carbon residue, full fraction (CCR) % (m/m) | - | 0.05，nax | 0.041 | SY2611-77 |
| Methyl alcohol, % (m/m) | - | 0.3，max | 0.2 | GC |
| Iodine number, % (m/m) | - | 115, max (to sewer oil, because of containing 1/3rd animal grease approximately, so value is temporarily by 1/3rd controls) | 85 | SY2114- 82 |
By table 4 data as seen, be 0.882 by the biofuel of waste edible oil ester methyl alcohol lactide generation except density is higher, other all properties all can reach the index request of GB diesel oil GB252-94 and German DIN-RME standard.
Description of drawings
Figure of description is catalytic esterification/lactide single stage method system biodiesel processes schema.
Claims (8)
1. preparation method that biofuel is a fatty acid methyl ester comprises: esterification that contained free fatty acids carries out with methyl alcohol under the special catalyst effect in pre-treatment, grease and the grease of the thick grease of animals and plants under special strong electrolyte and water effect and lactide reaction, and the methods such as refining purification of biofuel and glycerine.
2. described a kind of thick greasy pretreatment process of animals and plants that is used to prepare biofuel comprises: the adding strong electrolyte destroys the assorted system of glue earlier, then adds water hydratable and coagulates wadding gathering sedimentation, centrifugation then.Be characterized in special pretreatment reaction still, the thick grease of raw material is under 50～80 ℃ of normal pressures and abundant agitation condition, the using method that adds strong electrolyte and add the described strong electrolyte phosphoric acid of water hydratable is divided two kinds: at 50～80 ℃, best 60 ℃, and under fully stirring, a kind of is to add trace or i.e. 0.01～6.0% (m/m) on a small quantity, and high density i.e. 75～85% (m/m) phosphoric acid.Second kind is to add i.e. 20～50% (m/m) of volume, lower concentration i.e. 30～45% (m/m) phosphoric acid, with the peptized impurities in the thick grease of raw material, as phlegmatic temperament, organic phospholipid, protein, triglyceride, trickle food (in the non-oil in kind in the kitchen of especially eating) etc., the electric charge physical-chemical reaction takes place, make the charged separation of going ahead of the rest of these peptized impurities, then add 1～10% water and carry out aquation and make it flocculation and assemble, from grease, dissociate out.Adopt then heat sinkly fall, centrifugal or filtration process is removed, and can obtain comparatively ideal purification stock oil.
3. according to claim 2, the promptly corresponding acid of described strong electrolyte available period table pentels, the hydrate of nitrogen, phosphorus, arsenic, antimony, bismuth oxide compound, wherein best with the hydrate effect of the oxide compound of phosphoric.
4. according to claim 2, described special pretreatment reaction still is characterized in: the reactor that garden tubular jacketed type band stirs, can feed steam heating or thermal oil electrically heated in the chuck, and also can feed the cold water cooling.Its bottom is the butterfly end socket.Tube top, garden is provided with three opening for feeds, and the bottom is provided with clear liquor material discharge port, thermowell and manhole etc.Still top central authorities are provided with deceleration frame, cycloidal planetary gear speed reducer and agitator motor.Reactor inside is provided with the agitator of double-deck paddle.The reactor bottom is provided with discharging hole and the liquid material is extracted mouth etc. out.What extract that mouth links to each other out with the liquid material is tool awl end slurry tank, extracts with awl end slurry tank bottom liquid material that to manage what link to each other be a supercentrifuge out.
5. described a kind of esterification and lactide one-step technology that is used to prepare biofuel, be characterized in: the free fatty acids in the raw oil material can be separated in advance, but in special reaction kettle of the esterification under catalyst action, free fatty acids and grease are the triglyceride priority or carry out esterification and lactide reaction with methyl alcohol simultaneously that generating biofuel simultaneously is fatty acid methyl ester.At first, 100.0 parts of weights (100.0%) processing back sewer oil or animal-plant oil are added in the stirring tank at normal temperatures and pressures.Stir down 10～30%, the anhydrous methanol of best 21.0 parts of weights (21.0%, be equivalent to the value of four times of grease equivalents) adds in the reactor, and then adds basic catalyst 1～5.0%, best 1.5 parts of weights (1.5%).Slowly heating under ceaselessly stirring is to reflux temperature.Reflux and carried out esterification and lactide reaction in 1～3 hour,, separating methanol then.Feeding under the carbon dioxide conditions, add 1～5.0% then) atlapulgite under normal pressure, 80～90 ℃, stirred refining 1 hour.Simultaneously, the exhausted basic catalyst is neutralized by carbonic acid gas.Reaction product is carried out settlement separate, and lower floor is yellow glycerin layer, and the upper strata is biofuel, is yellow to light yellow, and bottom is the carclazyte of beige absorption.The upper strata biofuel is again through centrifugation, at last the qualified biofuel of complete clear, yield is 85～110%.
6. according to claim 5, described reaction kettle of the esterification is characterized in: the reactor that garden tubular jacketed type band stirs, can feed steam heating or thermal oil electrically heated in the chuck, and also can feed the cold water cooling.Its its top, bottom is provided with condenser and backflow dealcoholysis device.Its still pushes up a Side and is provided with reinforced sealing chamber, and still top central authorities are provided with deceleration frame, cycloidal planetary gear speed reducer and agitator motor.Its bottom is the reverse taper of 45 ° or 60 °, is convenient to discharge solid dregs such as carclazyte.Tube top, garden is provided with three opening for feeds, and the bottom is provided with clarification and looks into liquid material discharge port, thermowell and manhole etc.Reactor inside is provided with the agitator of double-deck paddle.The reactor bottom is provided with discharging hole and the liquid material is extracted mouth etc. out.What extract that mouth links to each other out with the liquid material is tool awl end slurry tank, extracts with awl end slurry tank bottom liquid material that to manage what link to each other be a supercentrifuge out.
7. described glycerine reclaims purifying technique, is characterized in adopting underpressure distillation dehydration purifying technique.Described underpressure distillation dehydration purification system is made up of underpressure distillation still, vacuum still, pumped vacuum systems and heating system etc.Raw glycerine is pumped to the underpressure distillation still, and described underpressure distillation still provides thermal source by thermal barrier heat-conducting oil furnace system or far-infrared electric system, can be satisfied with 250 ℃ temperature requirement.Vacuum still provides vacuum by liquid-ring vacuum pump, can be satisfied with the vacuum tightness requirement of 700mmHg.Described vacuum still has the degree of fractionation of 8～12 theoretical stages.
8. according to claim 1, free fatty acids and methyl alcohol contained in described grease and the grease carry out the used special catalyst of esterification/lactideization, oxyhydroxide for basic metal or alkaline-earth metal, with alkali-metal lower alcohol Gan, and by three class catalyzer such as the magnalium composite solid alkali metal hydroxide of hydrotalcite preparation or oxide compounds.
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