CN101223264A - Systems and methods for esterification and transesterification of fats and oils - Google Patents
Systems and methods for esterification and transesterification of fats and oils Download PDFInfo
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Abstract
Esterification and transesterification of fats and oils is conducted using one or more heterogeneous solid catalysts in the presence of an alcohol and a cosolvent. In one example, esterification of free fatty acids in fats and oils feedstock is conducted by contacting the feedstock with a solid catalyst having acidic groups. Transesterification of triglycerides in the feedstock is conducted by contacting the feedstock with a solid catalyst having basic groups. Single train continuous plant designs are described for near complete conversion of fats and oils by sequentially contacting the feedstock with heterogeneous acidic solid catalyst and basic solid catalyst.
Description
The cross reference of related application
The right of priority of the U.S. Provisional Application that the application requires to submit on June 9th, 2005 U.S. Provisional Application is submitted to number on October 18th, 60/688,818 and 2005 number 60/727,893, and the two at this all by quoting in full with as a reference.
Background of invention
Invention field
The present invention relates to be used for fat and the esterification of oil and the method and system of transesterify.
The explanation of correlation technique
Fat and oil mainly are made up of the triglyceride level and the free fatty acids of various ratios.These fat and oil are carried out esterification and/or transesterification reaction, can produce as the ester class of principal reaction product and the mixture of glycerine.The ester class of being produced can be used as biodiesel fuel or is used as the composition of other industrial application and the consumer's goods.
Be used at present fat and oil are transformed into many methods of ester class, comprise fat or oil with pure (for example methyl alcohol), miscible catalyzer and there is cosolvent to mix sometimes.The use of cosolvent can promote monophasic formation, prevent alcohol and fat or oil separating.Typically, be dissolved in the acid miscible homogeneous catalyst (for example sulfuric acid) in the alcohol, can be used for the esterification free fatty acids, and alkaline miscible homogeneous catalyst (for example sodium hydroxide or potassium hydroxide) can be used for the transesterify triglyceride level.Typically, these catalyzer can sequentially be used for two step processes.Heterogeneous catalyst also is used to use oil/fat and pure esterification and transesterification reaction, and still oil that takes place and alcohol are separated and can hinder speed of reaction significantly, therefore causes continuing the long residence time up to several hours, and causes low finished product output.
Summary
There is some difficulty in the application of described homogeneous catalyst.For example, typically by distillation remove in the reaction product residual pure and mild cosolvent; Therefore yet catalyzer is not to have volatilely, remains in the final product as impurity after distillation.According to the final product purity of expectation, need carry out expensive time-consuming additional process, to remove catalyst impurities.In addition, used the industrial equipments of homogeneous catalyst and must operate, so that duplication of production catalyzer liquid storage with batch processing mode.Described operation comprises a large amount of labor forces, workman crevice corrosion chemical and excessive loss repeatedly.Batchwise operation depends on operator's skill very much, causes inconsistent device operation and quality product through regular meeting.In addition, the synthetic metal of the application need costliness of corrosive acid is stood reactor, groove, pipe, valve, pump and other processing units of corrosive environment with preparation.Therefore, need improvement to be used for fat and the esterification of oil and the method and system of transesterify.
An embodiment disclosed herein comprises that this method comprises mixes raw material with pure and mild cosolvent from the method for oil or fatty feedstock production ester; The mixture of raw material, pure and mild cosolvent is contacted first solid heterogeneous catalyst that comprises acidic-group, to produce first reaction mixture; And first reaction mixture contact comprised second solid heterogeneous catalyst of basic group, to produce second reaction mixture.
Another embodiment disclosed herein, comprise and have first reactor (having comprised first solid catalyst that contains acidic-group), the ester production system of second reactor (having comprised second solid catalyst that contains basic group) and the pump that assembled, wherein first solid catalyst is suitable for the catalysis free fatty acids and is transformed into ester, second solid catalyst is suitable for catalyzing glycerol three esters and is transformed into ester, but and second reactor is communicated with (in fluid communication with) with the first reactor fluid, and the mixture that described pump can drive oil or fatty raw material and alcohol one after the other and continuously passes first reactor and second reactor.
Another embodiment disclosed herein, comprise the method that triglyceride level is transformed into one or more other ester class, comprising triglyceride level is mixed with pure and mild cosolvent, and with the mixture contact basic group anionite-exchange resin of triglyceride level, pure and mild cosolvent.
Another embodiment disclosed herein comprises the method that free fatty acids is transformed into one or more other ester classes.This method comprises: free fatty acids is mixed with pure and mild cosolvent, and mixture is contacted the acidic-group Zeo-karb.
Brief Description Of Drawings
Fig. 1 is the schema that is used to illustrate the embodiment method of the esterification of fat and oil and transesterify.
Fig. 2 is the synoptic diagram that illustrates the device design implementation example that is applicable to fatty and oily esterification and transesterify.
Embodiment
In one embodiment, use solid heterogeneous catalyst with the esterification that causes free fatty acids or the transesterify of triglyceride level, to produce ester from fat or oil.Use described solid catalyst rather than homogeneous catalyst, help separating catalyst from reaction mixture.For example, can remove solid catalyst, or it is retained in flow type (flow-through) reactor.In addition, can be in a continuous manner rather than batch processing mode operate the device that utilizes solid catalyst.In one embodiment, in the presence of pure and mild cosolvent, use solid heterogeneous catalyst to promote the esterification of free fatty acids with acidic-group.For example, but can use the hydrionic solid catalyst that has the acidic surface group or be suitable for providing catalytic esterification.In one embodiment, in the presence of alcohol, use solid heterogeneous catalyst, to promote the transesterify of triglyceride level with basic group.For example, but can use the solid catalyst that has the alkaline surface group or be suitable for providing the hydroxyl ion of catalyzed transesterification.In general, in some embodiments, acidic solid catalyst presents Lewis acid groups (Lewis acidic group) in its surface, or be suitable in reaction mixture, producing Lewis acid (Lewis acid), alkali solid catalyst presents Louis's base (Lewis basic group) in its surface, or is suitable for producing in reaction mixture Lewis base (Lewis base).In described embodiment, cosolvent is added reaction mixture, can promote the monophasic formation between fat and the alcohol, this greatly reduces resistance to mass transfer (mass transfer resistance) and accelerated reaction.
The raw material sources of free fatty acids and triglyceride level can be from the fat in any suitable animal, plant or algae source or oily.Limiting examples for described fat and oil source comprises rapeseed oil, plam oil, sunflower seed oil, soya-bean oil, cocounut oil, oleum gossypii seminis, Viscotrol C, manioca (Jatropha) seed oil, Pongamia glabra (Pongamia) seed oil, butter (Yellow Grease), exhausted frying oil, tallow and animal tallow.
By the schema among Fig. 1, for example understand a kind of case method that is used for fatty or oily raw material are transformed into ester.In square frame 10, at first raw material is mixed with alcohol.In square frame 15, randomly cosolvent is added in the feedstock/alcohol mixture, to promote monophasic formation.The use of cosolvent can advantageously reduce process is become complicated and reduce the alcohol and fat and separating of oil possibility that reacts.Can use any cosolvent that is suitable for promoting the formation of single-phase mixture.Limiting examples comprises tetrahydrofuran (THF) (THF), 1, and 4-dioxan, diethyl ether, methyl tertiary butyl ether (methyltertiarybutylether, MTBE) and isopropyl ether (diisopropylether).And then in square frame 18, randomly raw mix is heated to the fs temperature of reaction of expectation.In square frame 20, raw mix is contacted with the solid catalyst that comprises acidic-group.In the presence of catalyzer disclosed herein, free fatty acids and triglyceride level in alcohol and the raw material react the production ester output.In certain embodiments, alcohol is for example monobasic alkanol of alkanol, and ester products is an alkyl ester.In certain embodiments, alkanol is C
1-4The monobasic alkanol (as, methyl alcohol or ethanol).In square frame 25, resulting mixture in the reaction that square frame 20 carries out randomly heats or is cooled to the subordinate phase temperature of reaction of expectation.In square frame 30, mixture is contacted with second solid catalyst that comprises basic group at last.
According to specific embodiment, in the process shown in the schema of Fig. 1, can add or leave out some steps.For example, in the embodiment of improvement, by distillation or other equivalent method, pure and mild cosolvent from the reaction mixture excessive separation, use centrifugal, gravity settling or other equivalent method, separate ester, and the washing ester is with acquisition high purity ester from by-product glycerin.Randomly, respectively dry ester and glycerine are to obtain even high level of purity more.In addition, according to application, the order of rearrangeable step.
In one embodiment, ester products is as the biodiesel fuel of running diesel engine.The non-limiting purposes of other of ester comprises the rocket engine fuel of flyer; Be used to start the fuel of turbine, compressor, pump and generator; The lubricating oil of lubricant that comprises the drilling operation of nontoxicity and the biodegradable rig that for example is used to relate to the land and water substrate; Fuel dope; Lubricating grease; Perfume compound; Medicine; Printing ink; Foodstuff additive; Makeup; And healthcare product.
Be substantially free of in the embodiment of the fat of free fatty acids or glyceride stock in some uses, only use solid catalyst with basic group.On the contrary, only use the catalyzer that contains acidic-group, can transform the raw material that only comprises free fatty acids basically.In some embodiments, use two or more solid catalysts serially.For example, in the raw material of the mixture that comprises free fatty acids and triglyceride level, at first the raw material contact had the solid catalyst of acidic-group, so that free fatty acids is transformed into alkyl ester.After reacting in the presence of first catalyzer, then the reaction product contact had the solid catalyst of basic group, triglyceride level is transformed into alkyl ester and glycerine.
In one embodiment, the solid catalyst of use described herein is immiscible basically, and is insoluble to for example tetrahydrofuran (THF) (THF) of methyl alcohol, fat, oil and/or cosolvent basically.In some embodiments, solid catalyst comprises the essentially no active carrier of being used for fixing reactive group (for example acidity or basic group).The limiting examples of suitable solid catalysts comprises ion exchange resin, carrier lipase or other suitable katalaze enzyme, carrier or non-carrier metal or metal oxide, and other immobilized acidity or basic group.In one embodiment, the solid catalyst that contains acidic-group is a Zeo-karb.Can use to reaction mixture hydrionic described resin is provided.Similarly, in one embodiment, the catalyzer that contains basic group is an anionite-exchange resin, and it is used to reaction mixture that hydroxyl ion is provided.Be used to support the suitable matrix of immobilized catalytic group, comprise carrier based on zeolite or other silica or aluminum oxide, graphite material for example activated carbon, rock or stone, timber or from other organic substance of plant or animal, and synthon or plastics.Catalyst solid can be any suitable shape, comprises that spherical, cylindric, cubes, annular shape, ellipticity, fibrous, textile-like, compression are laminar, and irregularly shaped.In some embodiments, solid adopts powdery, particulate state, kibbles the abrasive dust shape or the form of the material of carefully milling.In some embodiments, by using highly porous matrix or fabric fibre matrix, improve the active surface zone of solid catalyst.Increase surface-area, can allow to reduce temperature of reaction and pressure, and reduced equipment sizes.
Usually, under barometric point, implement esterification and transesterification reaction.Under these pressure, temperature of reaction from about 40 ℃ to about 65 ℃, can not seethed with excitement to guarantee reaction mixture usually.By improving temperature of reaction, can reach speed of reaction faster.By under high pressure carrying out this reaction, can reach higher temperature.Therefore in one embodiment, to the pressure of about 5000kPa specification, carry out reaction process as herein described in about 50kPa specification.In another embodiment, to the pressure of about 5000kPa specification, implement reaction process as herein described in about 1000kPa specification.Under these pressure, can use the temperature of reaction between 50 ℃ to about 300 ℃, obtain conversion rate faster.Can select suitable reaction pressure and temperature according to the ratio of solvent and reactant in the boiling point of the composition in the reaction mixture and the mixture.Pressure and temperature can improve according to the fat that is comprised, oil, other liquid, and catalyzer can stably exist and can not degrade.By under high temperature and high pressure, implementing reaction, can reach higher speed of reaction.Higher speed of reaction has reduced the residence time that needs in the reactor, causes reactor size to become littler.In one embodiment, the residence time in the given reactor less than one hour (as, about 10 to about 30 minutes).
Some embodiments comprise the system that is used to implement reaction as herein described and method.For example, can use production unit with one or more reactors that are used to continous processing system is provided and assemble.In some embodiments, continous processing system has single continuous structure and two or more placed in-line reactor.In a described embodiment, will by oil or fat, alcohol (as, methyl alcohol or ethanol) and the reaction mixture of cosolvent composition be transported to first reactor that has been full of the heterogeneous acid surface catalyst of solid that is used for the esterification free fatty acids.Then, the reaction mixture that will discharge from first reactor is transported to second reactor of the basic surface solid heterogeneous catalyst that has been full of the subordinate phase transesterify that is used for triglyceride level.Can be under barometric point or vacuum flash distillation or distillation from the discharge of subordinate phase reactor, to reclaim excessive pure and mild cosolvent, stay the mix products of alkyl ester and glycerine subsequently.In some embodiments, the washing mix products is to promote being separated between ester and the glycerin layer.Washing also helps to extract dissolved glycerine in the ester.By gravity settling in vat or by using centrifugal or other separate apparatus, from glycerine, separate ester, to produce pure pure ester and purification of glycerol respectively.Can suitably introduce secondary filter, with reduce contaminated feedstock, other processes raw material or have the possibility of the solid catalyst of floating solid, thereby improve the ester quality.
Reactor design is become to have the packed bed that Continuous Flow is crossed the liquid reaction mixture of solid catalyst bed, realize no gap contact catalyst, to obtain high conversion.In other embodiments, type of reactor can be that fluidized-bed, moving-bed, circulation bed, elutriation bed, agitated bed, ebullated bed or other are designed for the adequate types of contact solid catalyst and liquid medium.In moving-bed, circulation bed or elutriation bed structure, continuous solid catalyst in Cyclonic is provided with, and feed back is in reactor.Type of solid catalyst and reaction mixture character are depended in the selection of type of reactor.In an example embodiment, under pressure and temperature, operate reactor based on envrionment conditions and expectation transformation efficiency.
Utilize in the embodiment (for example after Esterification Stage transesterify stage) of two phase process at some, each stage can be utilized the reactor more than.For example, in each step of reaction, can use two or more reactors, to promote the level of finishing of esterification and transesterification reaction.By the serial or parallel connection tube stub, can connect the set of reactors in each stage, to obtain the product yield level of expectation.In some embodiments, before being transported to downstream reactor, handle the process fluid of discharging from upstream reactor (as, wash), to separate and to remove moisture, glycerine and other by product of more not expecting that in upstream reactor, forms.Remove the byproduct of reaction of more not expecting in the intermediate steps, help quicker the finishing of reaction progress, thereby in the shorter residence time, realize higher ester conversion rate.
In some embodiments, can comprise the recycle system, wherein one or many ground uses pump or jet apparatus, reaction product is carried continuously get back to reactor inlet, to improve finished product output and purity.
Fig. 2 is that graphic extension is suitable for an illustrative device design used herein.This design comprises two filled columns (packed column) reactor 100 and 102.With solid catalyst filling reactor 100 as herein described and 102.Catalyzer can be the globular form.In one embodiment, spherical diameter with about 0.3mm to about 1mm.Other shape, for example cylindric, cone-shaped, cubes, or irregular randomly shaped, for example minute hand shape, weak point or macrofiber, sheet, netted, abrasive dust shape or the like also can be used for the packed column device.Also can be with the shape of Preparation of Catalyst imaging Raschig ring (Rashig ring), Pall ring (Pall ring), Bel's saddle ring (Berl Saddle) or other shape filler.Catalyzer can also be the form of structured packing.
By pump 104, at first pass heat exchanger 106, with reaction mixture (as, mixed pure and mild cosolvent fat or oily raw material) intake system.Heat exchanger 106 can be used for reaction mixture is heated to the preferred temperature that is suitable for the reaction in first column reactor 100.Proper site in single continuous system (as, the downstream of heat exchanger 106) can comprise one or more extra pumps 108, make and running through system flow and supercharging.In other embodiments, one or more extra pumps 108 are arranged on position in the reaction system outside shown in Figure 2.
The tempering tank 109 of outer wrap is attached to pump 104, makes pump suction that reaction mixture is imported the reactor assembly from tempering tank.In one embodiment, tempering tank 109 is equipped with the air operated vibrator.Also can use the tempering tank of other type and other hybrid system (as, use by electric motor driven vibrator or static mixer).Before being inhaled in the reactor assembly by pump 104, mixing raw material, pure and mild cosolvent in water jacket 109.In one embodiment, operating pumps 104 and reactor 100 and 102 between about 50psi and 600psi specification, yet, can use other pressure as required.
Before in importing tempering tank 109, but pre-treatment fat and oily.In some embodiments, before large quantities of storage raw materials, implement pretreatment operation.Perhaps, when being pumped into before other downstream processing unit (plant) when from batch storage (as, tempering tank 109), extracting raw material, need not many processing and can preserve raw material, and carry out pre-treatment with good conditionsi.In some embodiments, pre-treatment comprises melts fat, makes them easier to be processed.Also can use instrument to purify raw material, to separate not saponifiable matter.In some applications,, can produce the more product of good quality, thereby reduce or need not product refining instrument by the beginning that cleaner raw material carries out.Pretreatment operation comprises precipitation, decant and filtration, to remove free water content and suspended solids.Also can comprise drying subsequently, so that separate and remove emulsified water or combination water and other volatile compound.Can be in vacuum-evaporator, or, implement drying operation by utilizing solid drying medium with the form of packed bed or thermopnore or moving-bed.By utilizing suitable contact arrangement and separating device, also can use any suitable liquid dried medium.In some embodiments, with raw material with before pure and mild cosolvent mixes, make total moisture content be less than about 500ppm.Low moisture content in the raw material can be promoted higher the finished product purity.In some embodiments, in importing tempering tank 109 before, come unstuck, the oil in bleaching and the purification raw material.In certain embodiments, handle oil ﹠ fat, with the organic matter of absorption and separate dissolved, for example protein, sterol, hormone or the like.In other embodiments, before raw material is applied to main reactor, use for example positively charged ion and anionic exchange medium, handle oil ﹠ fat, with the inorganic salt and the free radical of absorption or exchange and separate dissolved.
In some embodiments, the preprocessing process of raw material also comprises the film that is used to filter and remove mixable homogenous contaminants.Can use and be used for separating the film that the cholesterol that is present in animal and plant fat and oil, sterol, steroid, hormone, protein and other can not be saponified.Reduce impurities in raw materials concentration, help to obtain higher output and purer product.
As shown in Figure 2, comprise strainer 110, with any residual particles material in the reaction mixture before removing in mixture being imported first column reactor 100.In the upstream of second column reactor 102, comprise second heat exchanger 112, make the fluid temperature (F.T.) ground regulation and control that can be independent of first reactor 100 flow into the fluid temperature (F.T.) of second reactor 102. Heat exchanger 106 and 112 is designed, make process fluid flow in pipe, simultaneously heating/heat-eliminating medium (as, water or steam) flow through outer tube/shell, or vice versa.As required, can use the heat exchanger (for example, plate-type heat exchanger, spiral heat exchanger) of other type.
Separate suitable pipe or conduit with the valve of Flow-rate adjustment by having suitable being used to, heat exchanger 106 and 112, reactor 100 and 102, pump 108 and strainer 110 form with single string can be interconnected.But the alternative structure of using system parts also.Can equip pressure warning unit and thermometer in place.According to circumstances, equipment is used to control the Other Instruments of the method for operate continuously.
If expectation uses hyperchannel to improve output and purity, can comprise optional recycle circuit 114, turn back to first heat exchanger 106 with product with second reactor 102.Sometimes, the recirculation of reactor output terminal can be got back to the input terminus of same reactor, to improve the quality of products.After final reaction product is left reactive system, can use refining unit with separate solid and liquid impurity.Use suitable strainer, cyclone separator, hydrocyclone or whizzer, separate solid and liquid.By using absorption, or Solid Bed adsorbs, or by using the liquid-liquid extraction technology, or by washing, separable miscible liquid impurity.Gravity settling tank or whizzer be can use, immiscible fluid, for example alkyl ester and glycerol product separated.Refining also can comprise the use desiccating method, uses or do not use vacuum simultaneously.In all situations, randomly refining unit is assembled into single successive mode, make whole process operate in a continuous manner.In one embodiment, the methyl esters that produced and the mixture storage of glycerine in the processing are existed in the vat, allowing to carry out gravity separation, or use whizzer to handle, to obtain methyl esters and glycerine respectively.
Embodiment
Embodiment 1-transforms the spent ion exchange resin chamber of experimentizing
To adorn the Lakeside Packers of factory from Steamed dumplings with beef, the animal tallow of Brooks AB (yellow grease) is as former fat raw material.Animal tallow contains less than 1% moisture and about 1% free fatty acids.For the higher free fatty acid content in the simulated fat, 99% pure oleic acid is added in the animal tallow, to reach the free fatty acids fatty consistency of 15%w/w.The laboratory cylindrical pressure kettle (2L capacity) of standard is used for reactor.High-pressure sterilizing pot have be used to mix, the equipment of electrically heated, water cooling and pressurized contents.Use high pressure nitrogenize bottle, pressure kettle is pressurizeed.
The animal tallow that 100 grams is contained the 15%w/w free fatty acids places the 2L round-bottomed flask.The methyl alcohol and the 336 gram THF that add 60: 1 ratios, and thorough mixing becomes single-phase.Employed methyl alcohol and THF have the purity above 99%.Whole inclusion of round-bottomed flask are transferred in the high-pressure sterilizing pot, and added 375 gram strong-acid cation-exchange resins (available from the US FILTER of C381BH
).During with 600rpm operation agitator, high-pressure sterilizing pot is pressurized to 2068kPa specification (300psi specification), and 120 ℃ of heating 1 hour.Then, pour the high-pressure sterilizing pot inclusion into vacuum filter, to leach cation exchange resin catalyst.In the subordinate phase reaction, permeate is transferred in the clean high-pressure sterilizing pot, and added 375 gram strongly basic anion exchange resins (available from US FILTER
A674BOH).During with 600rpm operation agitator, mixture is pressurized to 2068kPa specification (300psi specification), and 60 ℃ of heating 1 hour.After 1 hour, all inclusion of high-pressure sterilizing pot are transferred in the vacuum filter, to separate anion-exchange resin catalyst.Then, permeate is transferred in the round-bottomed flask, and be fixed on vacuum wheel commentaries on classics steam (roto-vap) separator, to distill out excessive methyl alcohol and THF.After about 10 minutes, isolating glycerin layer and ester layer appear in round-bottomed flask.Then, centrifugal inclusion, and from the ester layer on the glycerine decant top that remains lower floor.Further do not handle, on the Hewlett-Packard gas chromatographicanalyzer, analyze the methyl esters sample.Obtain showing the result who surpasses 99.9% transformation efficiency.The mol ratio of methyl alcohol to fat depended in conversion reaction at least in part.For example, in one embodiment, methyl alcohol to fat the mole between about 10: 1 and about 60: 1, cause the turnover ratio between about 85% and about 99.9%.
By 689kPa specification (100psi specification) to the pressure of 2068kPa specification (300psi specification) scope, 50 ℃ to 120 ℃ temperature, the methyl alcohol mol ratio of 40: 1 to 60: 1 scopes, and 30 minutes residence times to 60 minutes scopes, carry out repeated experiments.Ester conversion rate reaches about 90% to about 100% scope.High pressure, high temperature, high methanol ratio and high residence time, bring speed of reaction faster usually.Use also can implement to have the experiment of analog result from the vegetables oil of restaurant's recovery with from soybean, corn, Sunflower Receptacle and canola oil.Also use ethanol rather than methyl alcohol, experimentize, obtain to surpass 95% transformation efficiency.
Embodiment 2-experimental installation
Use two filled column reactors, the continuous plant of the single string of preparation.With the storng-acid cation exchange resin of 10 liters of about 0.3mm sphere diameter forms (available from US FILTER
C381BH) fill first reactor.The strongly basic anion exchange resin of also using 10 liters of 0.3mm to 1mm sphere diameter forms is (available from US FILTER
A674BOH) fill second reactor.Two pillars all are that the diameter of surveying is 4 inches (4 ") and length are 5 feet (5 '), and (overcoat of 6 ") is to provide temperature control all to have equipped 6 inches of diameters around their whole pipeline section.Heat exchanger has all been equipped in upstream at two reactors.Forming the series connection form of single string, ligation post and heat exchanger, and by 1/2 " are managed and the needle-valve that is used for isolating suitable ball valve and is used for Flow-rate adjustment interconnects.By the whole assembly (it is highly measured and is about 8 feet (8 ')) on 7 legs that are placed in 3 leg base next doors, all posts of vertical fixing.Use the reciprocating piston pump of air-operated drive, assembly is carried out feed.
By thawing, filtration and vacuum-drying, animal tallow is carried out pre-treatment.The tempering tank of jacket is heated to about 50 ℃, add fat, methyl alcohol and the THF of fusing then, mild agitation simultaneously.Mixture is made up of 6000 gram animal tallows with molar ratio range THF between 10 to 15 at methyl alcohol between 40 to 60 and molar ratio range.
Use steam, preheating first reaction column, and remain between 80 ℃ to 120 ℃.Preheating second reaction column, and remain between 50 ℃ to 60 ℃.Then, by with compressed air delivery in pump, reaction mixture is pumped in the testing apparatus.Offer the compressed-air actuated pressure of pump by regulation and control, the regulation and control pumping capacity.At first reaction mixture is passed through by steam-heated heat exchanger.At heat exchanger outlet, reaction mixture temperature reaches 120 ℃, and can overflow and enter the first reactor catalyst bed.The flow velocity of conditioned reaction mixture is to reach the flow velocity of about 10L/hr.
Leave after first reaction column, reaction mixture overflows into use as the water of heat-eliminating medium and be cooled to 60 ℃ second heat exchanger.Mixture enters second reaction column subsequently.Flow velocity through second reactor is identical with the flow velocity maintenance in first reactor, can prepare single continuous system thereby need not circulation.
To be fixed on the two stage needle valve system on the reactor removal device (discharge), be used for the counterpressure of control test device, and product fluid will be discharged in the barometric point as blow-off valve.Testing apparatus from the pump discharge to terminal blow-off valve is maintained at about the 300psi specification.Reactor product is entered in the portable bucket.Then, evaporate to dryness product mixture under the vacuum to separate and to reclaim methyl alcohol and THF, stays the mixture of methyl esters and glycerine subsequently.Then, filtering mixt to be removing solid precipitation from fat, and carry out centrifugal, to separate methyl esters from glycerine.The supernatant liquid of decanting centrifuge is to obtain to be suitable for the almost pure alkyl ester as biofuel.
Although described the present invention as a reference according to embodiment and embodiment, should be appreciated that on the basis that does not break away from spirit of the present invention, can carry out many and various modifications to the present invention.
Claims (49)
1. one kind prepares the method for ester from fatty raw material, comprising:
Raw material and alcohol and cosolvent are mixed together;
With the mixture of raw material, alcohol and cosolvent, contact comprises first solid catalyst of acidic-group, to produce first reaction mixture; With
First reaction mixture is contacted second solid catalyst that comprises basic group, to produce second reaction mixture.
2. the method described in the claim 1, wherein fatty raw material is the material that is selected from the group of one or more oil, one or more fat and composition thereof.
3. the method described in the claim 1 also is included in first reaction mixture and contacts before second solid catalyst, remove in first reaction mixture to one or more compositions of small part.
4. the method described in the claim 1, wherein alcohol is C
1-4Alkanol.
5. the method described in the claim 1, wherein alcohol is methyl alcohol or ethanol.
6. the method described in the claim 1, wherein first solid catalyst comprises Zeo-karb.
7. the method described in the claim 1, wherein second solid catalyst comprises anionite-exchange resin.
8. the method described in the claim 1 is wherein mixed and is comprised that the use cosolvent is with the manufacture order phase mixture.
9. the method described in the claim 1, wherein cosolvent is a tetrahydrofuran (THF).
10. the method described in the claim 1, wherein in about 50kPa specification to the pressure between about 5000kPa specification, the mixture of raw material, alcohol and cosolvent is contacted first solid catalyst.
11. the method described in the claim 1 wherein under the pressure of about 1000kPa specification between about 5000kPa specification, contacts first solid catalyst with the mixture of raw material, alcohol and cosolvent.
12. the method described in the claim 1 wherein under the pressure of about 50kPa specification between about 5000kPa specification, contacts second solid catalyst with first reaction mixture.
13. the method described in the claim 1 wherein under the pressure of about 1000kPa specification between about 5000kPa specification, contacts second solid catalyst with first reaction mixture.
14. the method described in the claim 1 wherein will contact less than 1 hour for arbitrarily the raw material of certain portions with first solid catalyst.
15. the method described in the claim 1 wherein will contact less than 1 hour for arbitrarily first reaction mixture of certain portions with second solid catalyst.
16. the ester production system comprises:
First reactor comprises first solid catalyst that contains acidic-group, and wherein first solid catalyst is suitable for promoting that free fatty acids changes into ester;
Second reactor comprises second solid catalyst that contains basic group, and wherein second solid catalyst is suitable for promoting that triglyceride level changes into ester, but and second reactor be communicated with the first reactor fluid; With
Be used to drive the pump that the mixture of oil or fatty raw material and alcohol assembles by first reactor and second reactor continuously.
17. the system described in the claim 16 also comprises one or more extra reactors, wherein comprises first solid catalyst that is communicated with the first reactor fluid.
18. the system described in the claim 16 also comprises one or more extra reactors, wherein comprises second solid catalyst that is communicated with the second reactor fluid.
19. the system described in the claim 16 wherein by the tube stub between first reactor and second reactor, provides the fluid channel between first reactor and second reactor.
20. the system described in the claim 16 wherein first solid catalyst comprises Zeo-karb.
21. the system described in the claim 16 wherein second solid catalyst comprises anionite-exchange resin.
22. the system described in the claim 16, wherein first reactor comprises column reactor, fixedly packed bed, fluidized-bed, ebullated bed (bubbling bed), bubbling bed, ebullated bed (boiling bed), moving-bed, elutriation bed, circulation bed, agitated bed, or its combination.
23. the system described in the claim 16, wherein second reactor comprises column reactor, fixedly packed bed, fluidized-bed, ebullated bed (bubbling bed), bubbling bed, ebullated bed (boiling bed), moving-bed, elutriation bed, circulation bed, agitated bed, or its combination.
24. the system described in the claim 16 also comprises being used for heating or cooling off the heat exchanger that fluid assembled that flows at least one first reactor and second reactor.
25. the system described in the claim 16, also comprise and be used for heating or cooling off first heat exchanger that fluid assembled that flows into first reactor, flow into second heat exchanger that second reactor is assembled with being used to heat or cool off, wherein heat exchanger is assembled, make the fluidic temperature of supplying with first reactor be different from the fluidic temperature of supplying with second reactor.
26. triglyceride level is transformed into the method for one or more other esters, comprises:
Triglyceride level and pure and mild cosolvent are mixed together; With
With the mixture of triglyceride level, alcohol and cosolvent, contact anionite-exchange resin.
27. the method described in the claim 26, wherein alcohol is C
1-4Alkanol.
28. the method described in the claim 26, wherein alcohol is methyl alcohol.
29. the method described in the claim 26 is wherein mixed and is comprised fat or oily raw material and pure and mild cosolvent are mixed together.
30. the method described in the claim 26 wherein mixes producing single-phase mixture.
31. the method described in the claim 26, wherein cosolvent is a tetrahydrofuran (THF).
32. the method described in the claim 26 wherein under the pressure of about 50kPa specification between about 5000kPa specification, contacts anionite-exchange resin with the mixture of triglyceride level, alcohol and cosolvent.
33. the method described in the claim 26 wherein under the pressure of about 1000kPa specification between about 5000kPa specification, contacts anionite-exchange resin with the mixture of triglyceride level, alcohol and cosolvent.
34. the method described in the claim 26 wherein will be transformed into one or more other esters at least about 90% triglyceride level.
35. the method described in the claim 26 wherein will be transformed into one or more other esters at least about 95% triglyceride level.
36. the method described in the claim 26 wherein will be transformed into one or more other esters at least about 99% triglyceride level.
37. the method described in the claim 26 wherein will contact less than 1 hour for arbitrarily the mixture of triglyceride level, alcohol and the cosolvent of certain portions with anionite-exchange resin.
38. free fatty acids is transformed into the method for one or more other esters, comprises:
Free fatty acids and pure and mild cosolvent are mixed together; With
With the mixture of free fatty acids, alcohol and cosolvent, the contact Zeo-karb.
39. the method described in the claim 38, wherein alcohol is C
1-4Alkanol.
40. the method described in the claim 38, wherein alcohol is methyl alcohol.
41. the method described in the claim 38 is wherein mixed and is comprised fat or oily raw material and pure and mild cosolvent are mixed together.
42. the method described in the claim 38 wherein mixes to produce single-phase mixture.
43. the method described in the claim 38, wherein cosolvent is a tetrahydrofuran (THF).
44. the method described in the claim 38 wherein under the pressure of about 50kPa specification between about 5000kPa specification, contacts Zeo-karb with the mixture of free fatty acids, alcohol and cosolvent.
45. the method described in the claim 38 wherein under the pressure of about 1000kPa specification between about 5000kPa specification, contacts Zeo-karb with the mixture of free fatty acids, alcohol and cosolvent.
46. the method described in the claim 38 wherein will be transformed into one or more other esters at least about 90% free fatty acids.
47. the method described in the claim 38 wherein will be transformed into one or more other esters at least about 95% free fatty acids.
48. the method described in the claim 38 wherein will be transformed into one or more other esters at least about 99% free fatty acids.
49. the method described in the claim 38 wherein will contact less than 1 hour for arbitrarily the mixture of free fatty acids, alcohol and the cosolvent of certain portions with Zeo-karb.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68881805P | 2005-06-09 | 2005-06-09 | |
| US60/688,818 | 2005-06-09 | ||
| US60/727,893 | 2005-10-18 |
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| CN101223264A true CN101223264A (en) | 2008-07-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200680022924 Pending CN101223264A (en) | 2005-06-09 | 2006-06-09 | Systems and methods for esterification and transesterification of fats and oils |
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| CN (1) | CN101223264A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962599A (en) * | 2010-05-28 | 2011-02-02 | 王金华 | Complete equipment for refining commercial grease by utilizing illegal cooking oil and method thereof |
| CN102816645A (en) * | 2012-09-14 | 2012-12-12 | 天津工业大学 | Continuous preparation method of biodiesel |
| CN105038994A (en) * | 2015-07-28 | 2015-11-11 | 上海艾澜达泵业有限公司 | Method and system preparing biodiesel through utilizing waste edible oils and fats |
| CN108929788A (en) * | 2018-07-12 | 2018-12-04 | 佳力士添加剂（海安）有限公司 | A kind of method of catalyzing cation exchange resin preparation diglyceride |
-
2006
- 2006-06-09 CN CN 200680022924 patent/CN101223264A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962599A (en) * | 2010-05-28 | 2011-02-02 | 王金华 | Complete equipment for refining commercial grease by utilizing illegal cooking oil and method thereof |
| CN102816645A (en) * | 2012-09-14 | 2012-12-12 | 天津工业大学 | Continuous preparation method of biodiesel |
| CN105038994A (en) * | 2015-07-28 | 2015-11-11 | 上海艾澜达泵业有限公司 | Method and system preparing biodiesel through utilizing waste edible oils and fats |
| CN108929788A (en) * | 2018-07-12 | 2018-12-04 | 佳力士添加剂（海安）有限公司 | A kind of method of catalyzing cation exchange resin preparation diglyceride |
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