CN103074123B - A kind of preparation method of biofuel - Google Patents
A kind of preparation method of biofuel Download PDFInfo
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- CN103074123B CN103074123B CN201310007054.6A CN201310007054A CN103074123B CN 103074123 B CN103074123 B CN 103074123B CN 201310007054 A CN201310007054 A CN 201310007054A CN 103074123 B CN103074123 B CN 103074123B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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 present invention relates to a kind of preparation method of biofuel, comprising: make raw oil material under the existence of extra free-fat acid source with C
1~ C
6monohydroxy-alcohol reacts in the reactor, and separating out fat acid esters is to obtain biofuel from reacted material, and the content of described free-fat acid source free fatty acid is 2 ~ 100wt%, and higher than the content of raw oil material free fatty acid.The inventive method can improve biofuel yield and the purity of the low raw oil material of reactive behavior, and adaptability to raw material is strong.
Description
The application is the divisional application of 200610165101.x.
Technical field
The present invention relates to and react by grease and monohydroxy-alcohol the method preparing biofuel.
Background technology
The main component of biofuel is fatty acid ester, carry out transesterification reaction by grease and monohydroxy-alcohol to obtain, in the product of transesterification reaction except fatty acid ester, also may contain mono-glycerides, two sweet esters, glycerin by-products, and unreacted alcohol and glyceride stock.In prior art, the preparation method of biofuel can be divided into acid catalyzed process, base catalysis method, enzyme catalysis method and supercritical methanol technology.
CN1473907A adopts the tankage of vegetable oil refining and edible refiltered oil to be raw material, catalyzer forms by sulfuric acid, hydrochloric acid, tosic acid, Witco 1298 Soft Acid, naphthene sulfonic acid etc. are inorganic and organic acid is composite, produce through operations such as acidifying removal of impurities, continuously dehydrating, esterification, layering, underpressure distillation, the pressure of continous vacuum dehydration is 0.08 ~ 0.09MPa, temperature 60 ~ 95 DEG C, dehydration is to water-content less than 0.2%, the add-on 1 ~ 3% of esterif iotacation step catalyzer, esterification temperature 60 ~ 80 DEG C, 6 hours reaction times.Reaction after product first neutralizes removing catalyzer, and then layering is except anhydrating, and product obtains biofuel through underpressure distillation.Be that speed of response is slow with described acid catalysis Problems existing, have a large amount of spent acid and produce, contaminate environment.
DE3444893 discloses a kind of method, with mineral acid as catalyzer, under condition of normal pressure, at 50 ~ 120 DEG C, free fatty acids and alcohol are carried out esterification, pre-esterification process is carried out to oil plant, then under base metal catalysts, carry out transesterification reaction, but the inorganic acid catalyst left over will be neutralized by alkali, the amount of base metal catalysts can increase.Adopt pre-esterification, make work flow elongated, facility investment increases, and energy consumption significantly rises, and loss of material is serious.In addition, also need a basic catalyst to remove from product, have a large amount of waste water and produce.
CN1472280A discloses a kind of method, and using fatty acid ester as acyl acceptor, under the existence of biological enzyme, catalysis biological carries out transesterification reaction production biofuel.Adopt enzyme catalyst exist deficiency be: long reaction time, efficiency are lower, and enzyme price is more expensive, and in high purity methanol easy in inactivation.
CN1141993C to disclose under one of both grease and alcohol are the condition of supercritical state and prepares the method for fatty acid ester in the absence of catalyst with grease and alcohol, and the method adopts batch tank reaction, is unfavorable for large-scale commercial production.
CN1111591C discloses a kind of grease and monohydroxy-alcohol reacts the method preparing fatty acid ester, and the method is at 270 ~ 280 DEG C, adopts tubular reactor successive reaction under 11 ~ 12MPa condition, and fatty acid methyl ester yield is 55 ~ 60%.
Can be found by above-mentioned prior art, middle high-pressure legal system for biofuel exist biofuel yield lower or adopt batch tank reaction, be unfavorable for the problem of large-scale commercial production.
Summary of the invention
The invention provides a kind of preparation method of biofuel, the method can improve biofuel yield.
The preparation method of biofuel provided by the invention, comprising: make raw oil material under the existence of extra free-fat acid source with C
1~ C
6monohydroxy-alcohol reacts in the reactor, and separating out fat acid esters is to obtain biofuel from reacted material, and the content of described free-fat acid source free fatty acid is 2 ~ 100wt%, and higher than the content of raw oil material free fatty acid.
Described grease, as occurred in term " raw oil material " and " high-acid value grease ", has general sense well known in the art, and be the general name of oil and fat, main component is fatty acid triglycercide.General normal temperature be liquid be called oil, normal temperature is solid or is semisolidly called fat (abbreviation fat).Described grease comprises vegetables oil and animal oil, also comprises from the oil plant in the material such as microorganism, algae in addition, even also comprises crude oil, waste grease and rotten grease etc.Wherein crude oil refers to the grease without not reaching product standard after refining or refining.Refining step includes but not limited to the operations such as matter, alkali refining, dephosphorization matter, decolouring, deodorization of coming unstuck.The unsaponifiables of high level can also be contained in grease.The example of vegetables oil includes but not limited to soybean oil, rapeseed oil, peanut oil, wunflower seed oil, plam oil, Oleum Cocois and comes from the material (comprising the tall oil produced in paper-making process) containing fatty group of the fruit of other various farm crop and wild plant, stem, leaf, limb and root.The example of animal grease includes but not limited to lard, butter, sheep oil, fish oil etc.The mixture of two or more greases can be used.
The content <50wt% of described raw oil material free fatty acid, preferred <30wt%, particularly preferably <20wt%.In one embodiment, raw oil material comprises plam oil.In another embodiment, raw oil material is waste grease.
Described C
1~ C
6monohydroxy-alcohol refers to the unitary fatty alcohol of carbonatoms between 1 ~ 6, can be saturated alcohol or unsaturated alcohol.The example of monohydroxy-alcohol includes but not limited to methyl alcohol, ethanol, n-propyl alcohol, Virahol, vinyl carbinol, butanols such as propyl carbinol, isopropylcarbinol, amylalcohol such as Pentyl alcohol etc.Single alcohol can be used, or use the mixture of two or more alcohol.Described monohydroxy-alcohol particular methanol, ethanol and butanols, more preferably methyl alcohol and ethanol, be in particular methyl alcohol.C
1~ C
6the mol ratio of monohydroxy-alcohol and raw oil material can be 3 ~ 60:1, preferably 4 ~ 12:1.
Described free-fat acid source can be free fatty acids, and it can be saturated or undersaturated, preferred C
10~ C
24saturated or unsaturated fatty acids, more preferably C
12~ C
18unsaturated fatty acids, it can have one or more double bond, preferably containing a double bond.The example of free fatty acids includes but not limited to Lignoceric acid, docosoic acid, arachic acid, nondecylic acid, stearic acid, margaric acid, palmitinic acid, pentadecylic acid, tetradecanoic acid, tridecanoic acid, lauric acid, undecanoic acid, capric acid, Decosahedaenoic acid, arachidonic acid, oleic acid, linolenic acid, linolic acid, undecylenic acid etc.Free fatty acids is particularly preferably oleic acid.Described free fatty acids exists with the amount relative to raw oil material 1 ~ 50wt%, preferably 2 ~ 40wt%.
Described free-fat acid source can also be high-acid value grease, such as crude oil or waste grease etc.The content of described high-acid value grease free fatty acid can be 5 ~ <100wt%, preferably 10 ~ 60wt%, and higher than the content of raw oil material free fatty acid.The weight ratio of raw oil material and high-acid value grease is 1:0.02 ~ 50, preferred 1:0.04 ~ 20, more preferably 1:0.06 ~ 10.High-acid value grease can be under the jurisdiction of same classification or different classes of with raw oil material.
Raw oil material under the existence of extra free-fat acid source with C
1~ C
6the reaction of monohydroxy-alcohol can optionally be carried out under the condition of basic cpd as catalyzer.Described basic cpd such as can be selected from the oxyhydroxide of IA and IIA race element in periodictable, alcoholate, oxide compound, carbonate, supercarbonate and aliphatic carboxylate, the oxyhydroxide of preferred sodium, potassium, magnesium, calcium and barium, alcoholate, oxide compound, carbonate, supercarbonate and C
12~ C
24soap, the more preferably oxyhydroxide of sodium and potassium, oxide compound, alcoholate and C
12~ C
24soap.The add-on of basic cpd can be 0.005 ~ 0.3wt% of grease weight, preferably 0.008 ~ 0.2wt%.
In the methods of the invention, tubular reactor can be adopted, grease and alcohol can be supplied to reactor separately, or be supplied to reactor by after their pre-mixings, before being supplied to reactor, available preheater is by material preheating, also directly reactor can be entered, if raw material directly enters reactor, so reactor had both played the effect of preheater, also played the effect of reactor.As adopted preheater, can by grease preheating together with after alcohol difference preheating or mixing.In reactor, temperature is 200-320 DEG C, is in particular 230-280 DEG C.In reactor, pressure is 5 ~ 12MPa, is in particular 6 ~ 10MPa, and under lower pressure, (as 5 ~ 7.5MPa) also can realize goal of the invention.In reactor, liquid hourly space velocity is 0.1 ~ 10h
-1, be in particular 0.5 ~ 6h
-1, be more particularly 1 ~ 3h
-1.
In the methods of the invention, the step of described separating out fat acid esters comprises:
(A) the mixed ester phase formed in reacted material and glycerine to be separated and subsequently from described mixed ester phase and optionally steam monohydroxy-alcohol respectively mutually from glycerine, or from reacted material, to steam monohydroxy-alcohol before the mixed ester formed in reacted material phase and glycerine being separated;
(B) the mixed ester phase that will process through above-mentioned steps (A), by distillation or rectifying, or by washing and the ester phase formed after washing being separated with aqueous phase and collects described ester phase, obtain high purity fatty acid ester, and optionally the glycerine processed through above-mentioned steps (A) is obtained glycerine by distillation.
The method steaming monohydroxy-alcohol in above-mentioned steps (A) can be rectifying or flash distillation under the condition of temperature < 150 DEG C at the bottom of still.Pressure can carry out under the condition being greater than normal atmosphere, normal pressure or a vacuum.
In above-mentioned steps (A), mixed ester phase and glycerine are separated and can be undertaken by sedimentation or fibrous bundle separator, carry out sharp separation preferably by fibrous bundle separator.Said fibrous bundle separator is made up of separator cartridge and receiving tank, is provided with the fibrous bundle of Stainless Steel Wire composition in separator cartridge.Mixed ester phase and glycerine phase mixture first flow through separator cartridge, then enter receiving tank layering, realize the separation of mixture.Separation condition is temperature 20 ~ 200 DEG C, preferably 40 ~ 100 DEG C, and pressure is greater than a normal atmosphere or normal pressure, such as 0.1 ~ 0.5MPa, preferably 0.1 ~ 0.3MPa, air speed 0.1 ~ 25h
-1, preferably 1 ~ 10h
-1, more preferably 1 ~ 5h
-1.For the reacting rear material that emulsification is serious, well point phase effect be reached, adopt settling process generally need place and spend the night, and adopt fibrous bundle separator can to complete within very short time, thus significantly improve velocity of separation and production efficiency.
In an embodiment in above-mentioned steps (B), the mixed ester phase that will process through above-mentioned steps (A), obtain high purity fatty acid ester by distillation, the distillation of described mixed ester phase is undertaken by vacuum rectification tower rectifying or thin-film evaporator.Make the mixed ester obtained from step (A) enter vacuum rectification tower mutually, tower reactor pressure is less than 0.1MPa, is preferably less than 0.01MPa, is more preferably less than 0.001MPa.Can not reflux, or control of reflux ratio is at 0.01 ~ 10:1, preferably 0.1 ~ 2:1, tower reactor or thin film evaporation actuator temperature are 100 ~ 300 DEG C, preferably 170 ~ 280 DEG C, more preferably 190 ~ 280 DEG C.The optional distillation of glycerine phase also can be carried out similarly by vacuum rectification tower rectifying described above or thin-film evaporator.
In another embodiment in above-mentioned steps (B), the mixed ester phase that will process through above-mentioned steps (A), by washing and the ester phase formed after washing being separated with aqueous phase and collects described ester phase, obtain high purity fatty acid ester, in washing, the add-on of water is 10 ~ 100wt% of mixed ester phasor, preferably 20 ~ 80wt%; The temperature of water is 25 ~ 100 DEG C, preferably 40 ~ 80 DEG C.Washing can be carried out once, also can be repeatedly.If the ester phase acid number obtained in step (B) is higher, alkaline matter can be added carry out alkali cleaning in water.The alkaline matter being selected from sodium carbonate, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, potassium hydroxide one or more can be used.Alkaline matter can add as an aqueous solution, and concentration is 5 ~ 40wt%, preferably 5 ~ 20wt%.Mixture after washing is divided into ester phase and aqueous phase again, and this can be undertaken by sedimentation, and be separated preferably by fibrous bundle separator, separation condition is temperature 20 ~ 150 DEG C, preferably 40 ~ 100 DEG C, and pressure is greater than a normal atmosphere or normal pressure, air speed 0.1 ~ 25h
-1, preferably 1 ~ 10h
-1, more preferably 1 ~ 5h
-1.
The inventive method may further include step (C): adopt secondary molecules rectifying through the mixed ester phase resistates (i.e. still raffinate) of distillation, to be separated mono-glycerides and two sweet esters from step (B), or, first order molecular rectifying is adopted through the mixed ester phase resistates of distillation, to steam mono-glycerides and two sweet esters from step (B), and be circulated to reactor inlet, carry out secondary reaction.More specifically, as hope obtain content of monoglyceride higher cut time, secondary molecules rectifying can be adopted, the still raffinate obtained from step (B) enters molecule rectifier unit, 5Pa is less than at pressure, preferably be less than 3Pa, under being more preferably less than or equaling 1Pa pressure, face temperatures 170 ~ 220 DEG C, preferably under 180 ~ 200 DEG C of conditions, the mono-glycerides cut that content is higher can be obtained, content of monoglyceride higher fraction can be used as oil product slip additive and uses, last running can enter second stage molecule rectifying, at above-mentioned pressure, face temperatures 200 ~ 290 DEG C, preferably under 220 ~ 250 DEG C of conditions, two sweet esters of higher degree can be obtained, these mono-glyceridess and two sweet esters can be used as raw material and are again circulated to reactor inlet, carry out secondary reaction.If do not need to obtain the higher mono-glycerides cut of content, available first order molecular rectifying, directly steam mono-glycerides and two sweet esters, they are circulated to reactor inlet, carry out secondary reaction.And heavy residue can be used as fuel.Molecule rectifying is reach the object being separated multiple component continuous multi-stage (or continuous many groups) also can be adopted to operate.
The inventive method can improve the biofuel yield of the low raw oil material of reactive behavior, the defect that the product acid number that the raw oil material overcoming higher acid value obtains is high, take mixing oil as the summation of yield apparently higher than yield when low activity is oily and high-acid value grease reacts separately of the biofuel of raw material, and the purity of fatty acid ester still can be ensured when feed processing capacity is higher, there is industrial application value.The inventive method adaptability to raw material is strong, to the high grease even containing higher unsaponifiables of acid number, capable of direct processing, saves the preprocessing process that operation is numerous and diverse, makes energy consumption, facility investment decline.In addition, use the inventive method, mono-glycerides, the two sweet esters organic substance higher with the boiling point contained in unrefined oil plant can be made effectively to be separated, the composition that can become fatty acid methyl ester in unrefined oil is utilized.
This technical process of the inventive method is simple, substantially without the three wastes, is conducive to environmental protection.
Embodiment
Further illustrate the present invention below by embodiment, but the present invention is not limited to this.The raw material hereinafter used is commercially available or easily can obtains according to techniques well known.
Comparative example 1
Be the refined soybean oil liquid hourly space velocity 1.2h of 0.7wt% by free fatty acid content
-1, the speed of methyl alcohol molar equivalent 5 is continuously provided in tubular reactor, temperature 280 DEG C in reactor, pressure 9.5Mpa, and reacting coarse product is after separation of methanol, glycerine, and rectification under vacuum steams biofuel, biofuel yield 47wt%.
Comparative example 2
Be 0.45wt%-rapeseed oil liquid hourly space velocity 1.2h by free fatty acid content
-1, the speed of methyl alcohol molar equivalent 7 is continuously provided in tubular reactor, temperature 272 DEG C in reactor, pressure 8Mpa, and reacting coarse product is after separation of methanol, glycerine, and rectification under vacuum steams biofuel, biofuel yield 61wt%.
Embodiment 1
To be that the hair soybean oil of 36wt% mixes by weight 0.3:1 with the rapeseed oil of comparative example 2 containing unsaponifiables 1.2wt%, free fatty acid content, fluid hourly space velocity 1.2h
-1, the speed of molar ratio of methanol to oil 7 is continuously provided in tubular reactor, temperature 272 DEG C in reactor, pressure 8MPa, reacting coarse product is after separation of methanol, glycerine, and rectification under vacuum steams biofuel, biofuel yield 92.2wt%, acid number 3.5mgKOH/g.Remain raffinate at the bottom of still and can be used as feedstock circulation to reactor feed mouth, carry out secondary reaction.The composition that can become fatty acid methyl ester in raw material is almost all converted to required product.
At identical conditions, the hair soybean oil being 36wt% with above-mentioned free fatty acid content is raw material, biofuel yield 87.2wt%, acid number 9.0mgKOH/g.
Embodiment 2
Will containing unsaponifiables 1.5wt%, free fatty acid content is that the Oleum Gossypii semen of 26wt% mixes by weight 1:1 with refined soybean oil in comparative example 1, fluid hourly space velocity 1.2h
-1the speed of molar ratio of methanol to oil 5 is provided in tubular reactor, temperature 272 DEG C in reactor, pressure 8.5MPa, reacting coarse product is after separation of methanol, glycerine, and rectification under vacuum steams biofuel, biofuel yield 91wt%, biofuel purity 99.3wt%, acid number 3.3mgKOH/g, free glycerol content 0.2wt%.Ester mutually in add 40 DEG C, 5% sodium carbonate solution washs, after washing, mixture enters fibrous bundle separator, at temperature 40 DEG C, liquid hourly space velocity 10h
-1, point ester output phase and aqueous phase, ester phase acid number 0.27mgKOH/g, free glycerol content 0.018wt%.Remain raffinate at the bottom of still and can be used as feedstock circulation to reactor feed mouth, carry out secondary reaction.
At identical conditions, the Oleum Gossypii semen being 26wt% with above-mentioned free fatty acid content is raw material, biofuel yield 86wt%, acid number 7.2mgKOH/g.
Embodiment 3
Be waste grease and the soybean oil of 14.3wt% by free fatty acid content, rapeseed oil mixes by weight 1:1:1, fluid hourly space velocity 1.2h
-1the speed of molar ratio of methanol to oil 5 is continuously provided in tubular reactor, temperature of reactor 320 DEG C, obtain fatty acid methyl esters under the condition of pressure 9MPa, the crude product of outflow reactor enters flashing tower, removes methyl alcohol and reclaim methyl alcohol, reuse < 150 DEG C.Leftover materials are entered the separator containing fibrous bundle, temperature 52 DEG C, liquid hourly space velocity 5h
-1, divide ester output phase, ester enters vacuum rectification tower mutually, at vacuum tightness 8mmHg, tower reactor 280 DEG C, under the condition do not refluxed, tower top obtains biofuel, purity 99.1wt%, biofuel yield 83.9wt%, acid number < 2.0mgKOH/g, still raffinate enters molecule rectifier unit, at residual voltage 5 ~ 6Pa, at hot face 190 DEG C, obtain the lighting end that content of monoglyceride is higher, residue high boiler material is entered secondary molecules rectifying, at residual voltage 2Pa, at hot face 240 ~ 244 DEG C, obtain lighting end, this part lighting end can be used as feedstock circulation to reactor feed mouth, carry out secondary reaction, the composition that can become fatty acid methyl ester in raw material is almost all converted to required product.
At identical conditions, the waste grease being 14.3wt% with above-mentioned free fatty acid content is raw material, biofuel yield 84.2wt%, acid number 4.7mgKOH/g.
At identical conditions, soybean oil, rapeseed oil are raw material, and biofuel yield is respectively 69wt%, 76wt%.
Embodiment 4
Be that the waste grease of 50wt% mixes by weight 0.2:1 with the rapeseed oil of comparative example 2 by free fatty acid content, oil plant liquid hourly space velocity 1.2h
-1, the speed of molar ratio of methanol to oil 6 is continuously provided in tubular reactor, temperature 272 DEG C in reactor, pressure 7.2MPa, reaction conversion ratio 100wt%, biofuel reaction yield 93wt%.Acid number 4.2mgKOH/g, outflow reactor crude product reduces pressure after 0.1 ~ 0.13MPa, and liquid enters fibrous bundle separator, temperature 30 DEG C, liquid hourly space velocity 5h
-1divide ester output phase and glycerine phase, ester phase is entered respective flashing tower mutually with glycerine, remove methyl alcohol < 150 DEG C and methyl alcohol is reclaimed, reuse, after steaming methyl alcohol, separate glycerine, mixed ester enters thin-film evaporator, at vacuum tightness 8mmHg, under the condition that temperature is 252 DEG C, steam biofuel, purity 99.2wt%, still raffinate to reactor feed mouth, carries out secondary reaction as feedstock circulation, and the composition that can become fatty acid methyl ester in raw material is almost all converted to required product.
At identical conditions, with above-mentioned waste grease for raw material, biofuel yield 90wt%.
Embodiment 5
Be that the Production from Raw Cottonseed Oil of 29.5wt% mixes by weight 40:1 with the rapeseed oil of comparative example 2 by free fatty acid content, oil plant liquid hourly space velocity 1.2h
-1, the speed of molar ratio of methanol to oil 6 is continuously provided in tubular reactor, temperature 272 DEG C in reactor, pressure 9.5MPa, outflow reactor crude product is after decompression, standing sedimentation, separate mixed ester phase and glycerine phase, mixed ester phase is entered respective flashing tower mutually with glycerine, under < 150 DEG C of conditions, successive flash vaporization goes out methyl alcohol respectively, vacuum rectification tower is entered mutually by steaming the mixed ester after methyl alcohol, at vacuum tightness 8mmHg, tower reactor 252 ~ 255 DEG C, under the condition of reflux ratio 1:1, tower top steams fatty acid methyl ester, purity can reach 99.5wt%, fatty acid methyl ester yield 86wt%, still raffinate enters molecule rectifier unit, at residual voltage 1Pa, at hot face 250 DEG C, topping processing.This part material can be used as feedstock circulation to reactor feed mouth, carries out secondary reaction.The composition that can become fatty acid methyl ester in raw material almost all becomes product.
Embodiment 6
Be 15wt% by free fatty acid content, be raw material containing the Oleum Gossypii semen of unsaponifiables 5wt%, add 10wt% oleic acid wherein, at oil plant liquid hourly space velocity 1.2h
-1, under the condition of methyl alcohol molar equivalent 4.5, they are continuously provided in tubular reactor, temperature 272 DEG C in reactor, pressure 8MPa, reacting coarse product is after separation of methanol, glycerine, carry out rectification under vacuum, biofuel yield 91.3wt%, acid number 3.5mgKOH/g.
Remain raffinate fatty acids methyl esters, mono-glycerides, two sweet esters at the bottom of rectifying still, can be used as feedstock circulation to reactor feed mouth, be reused after mixing with fresh feed.
Embodiment 7
Take free fatty acid content as 4.5wt%, be raw material containing the waste grease of unsaponifiables 1.2wt%, add 20wt% oleic acid wherein, at oil plant liquid hourly space velocity 1.2h
-1under the condition of methyl alcohol molar equivalent 5, they are continuously provided in tubular reactor, temperature 272 DEG C in reactor, pressure 7.4MPa, the crude product of outflow reactor enters rectifying tower after decompression, removes methyl alcohol and reclaim methyl alcohol, reuse < 150 DEG C.Leftover materials standing sedimentation, point ester output phase and glycerine phase, enter vacuum rectification tower mutually by ester, at vacuum tightness 8mmHg, tower reactor 251 ~ 255 DEG C, under the condition of reflux ratio 1:1, tower top steams biofuel, and fatty acid methyl ester can reach 99.5wt%, biofuel yield 78wt%., still raffinate enters molecule rectifier unit, at residual voltage 1Pa, at hot face 250 DEG C, and topping processing.This part material can be used as feedstock circulation to reactor feed mouth, carries out secondary reaction.The composition that can become fatty acid methyl ester in raw material almost all becomes product.
Adopt raw material, reaction conditions and separating step same as described above, during reaction, do not add oleic acid, the biofuel yield 45.9wt% obtained.
Embodiment 8
Take free fatty acid content as the plam oil of the oil plant of 0.35wt% be raw material, add 15wt% oleic acid wherein, at oil plant liquid hourly space velocity 1.2h
-1, under the condition of molar ratio of methanol to oil 8, they are continuously provided in tubular reactor, temperature 272 DEG C in reactor, pressure 8MPa, reacting coarse product outflow reactor is after being decompressed to 0.1-0.13MPa, enter the fibre bed containing fibrous bundle, temperature 40 DEG C, liquid hourly space velocity 7h
-1under condition, separate mixed ester phase and glycerine phase, mixed ester is entered rectifying tower mutually, remove methyl alcohol < 150 DEG C, and methyl alcohol is reclaimed, reuse.Leftover materials are entered the fibre bed containing fibrous bundle, temperature 40 DEG C, liquid hourly space velocity 7h
-1under condition, separate glycerine, ester carried out rectification under vacuum mutually, at vacuum tightness 5mmHg, under the condition that still temperature is 235 ~ 240 DEG C, carry out rectification under vacuum, biofuel yield 69.6wt%,
Remain raffinate fatty acids methyl esters, mono-glycerides, two sweet esters at the bottom of rectifying still, can be used as feedstock circulation to reactor feed mouth, be reused after mixing with fresh feed.The composition that can become fatty acid methyl ester in raw material almost all becomes product.
Adopt raw material, reaction conditions and separating step same as described above, during reaction, do not add oleic acid, the biofuel yield 34.9wt% obtained.
Embodiment 9
Take free fatty acid content as the soybean oil of 2.5wt% be raw material, add the unsaturated free fatty acids of 3wt%C16 wherein, at oil plant liquid hourly space velocity 1.2h
-1, under the condition of methyl alcohol molar equivalent 15, they be continuously provided in tubular reactor, temperature 300 DEG C in reactor, pressure 9MPa, reacting coarse product, after separation of methanol, glycerine, carries out rectification under vacuum, biofuel yield 72wt%.
Remain raffinate fatty acids methyl esters, mono-glycerides, two sweet esters at the bottom of rectifying still, can be used as feedstock circulation to reactor feed mouth, be reused after mixing with fresh feed.
Adopt raw material, reaction conditions and separating step same as described above, during reaction, do not add C
16unsaturated free fatty acids, the biofuel yield 55wt% obtained.
Claims (18)
1. improve a method for biofuel yield, comprising: make raw oil material under the existence of extra free-fat acid source with C
1~ C
6monohydroxy-alcohol reacts in the reactor, and separating out fat acid esters is to obtain biofuel from reacted material, and described free-fat acid source is free fatty acids, and described free fatty acids exists with the amount relative to raw oil material 1 ~ 50wt%; Or, described free-fat acid source is high-acid value grease, the content of described high-acid value grease free fatty acid is 5 ~ <100wt%, and higher than the content of raw oil material free fatty acid, the weight ratio of raw oil material and high-acid value grease is 1:0.02 ~ 50, in reactor, temperature is 200-320 DEG C, and in reactor, pressure is 5 ~ 12MPa, C
1~ C
6the mol ratio of monohydroxy-alcohol and raw oil material is 3 ~ 60:1, and in reactor, liquid hourly space velocity is 0.1 ~ 10h
-1.
2. in accordance with the method for claim 1, it is characterized in that, described free fatty acids is C
10~ C
24saturated or unsaturated fatty acids.
3. in accordance with the method for claim 1, it is characterized in that, described free fatty acids is C
12~ C
18unsaturated fatty acids.
4. in accordance with the method for claim 1, it is characterized in that, described free fatty acids is oleic acid.
5. in accordance with the method for claim 1, it is characterized in that, described free fatty acids exists with the amount relative to raw oil material 2 ~ 40wt%.
6. in accordance with the method for claim 1, it is characterized in that, the content of described high-acid value grease free fatty acid is 10 ~ 60wt%.
7. in accordance with the method for claim 1, it is characterized in that, described high-acid value grease is crude oil or waste grease.
8. in accordance with the method for claim 1, it is characterized in that, the weight ratio of raw oil material and high-acid value grease is 1:0.06 ~ 10.
9. in accordance with the method for claim 1, it is characterized in that, the content <50wt% of the free fatty acids of described raw oil material.
10. in accordance with the method for claim 1, it is characterized in that, the content <20wt% of the free fatty acids of described raw oil material.
11. in accordance with the method for claim 1, it is characterized in that, containing plam oil in described raw oil material.
12. in accordance with the method for claim 1, it is characterized in that, described raw oil material is waste grease.
13. in accordance with the method for claim 1, it is characterized in that, described C
1~ C
6monohydroxy-alcohol is methyl alcohol, ethanol or butanols.
14. in accordance with the method for claim 1, it is characterized in that, C
1~ C
6the mol ratio of monohydroxy-alcohol and raw oil material is 4 ~ 12:1.
15. in accordance with the method for claim 1, it is characterized in that, described reactor is tubular reactor.
16. in accordance with the method for claim 1, it is characterized in that, in reactor, temperature is 230-280 DEG C.
17. in accordance with the method for claim 1, it is characterized in that, in reactor, pressure is 5 ~ 7.5MPa.
18. in accordance with the method for claim 1, it is characterized in that, in reactor, liquid hourly space velocity is 0.5 ~ 6h
-1.
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| CN101633605A (en) * | 2008-07-23 | 2010-01-27 | 张伟民 | Method for preparing glycerin from byproduct in manufacture procedure of biodiesel |
| CN102061223B (en) * | 2010-12-02 | 2012-12-05 | 同济大学 | Method for preparing biodiesel |
| CN104745309B (en) * | 2013-12-27 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of method for improving biodiesel yield |
| CN105199857B (en) * | 2014-06-25 | 2019-04-16 | 中国石油化工股份有限公司 | A method of improving biodiesel yield |
| CN105647655B (en) * | 2014-11-26 | 2023-03-10 | 中国石油化工股份有限公司 | Method for preparing biodiesel |
| CN104774694A (en) * | 2015-04-08 | 2015-07-15 | 郑州凯山生化工程有限公司 | Method for synchronously preparing biodiesel and glycerol from high-acid-value vegetable oil |
| CN106010681A (en) * | 2016-06-28 | 2016-10-12 | 刘昱伶 | Composite biodiesel |
| CN105950299A (en) * | 2016-06-28 | 2016-09-21 | 梁红 | Biodiesel |
| CN105950300A (en) * | 2016-06-28 | 2016-09-21 | 刘昱伶 | Biodiesel |
| CN109423359B (en) * | 2017-08-30 | 2022-03-11 | 中国石油化工股份有限公司 | Method for stably preparing biodiesel |
| CN109971553A (en) * | 2017-12-27 | 2019-07-05 | 中国石油化工股份有限公司 | A method of improving biodiesel yield |
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| CN100439474C (en) * | 2005-09-30 | 2008-12-03 | 中国科学院山西煤炭化学研究所 | Method for preparing biological diesel oil by esterifying, ester interchanging greases in high acid number |
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