CN103725424B - A kind of production method of biofuel - Google Patents
A kind of production method of biofuel Download PDFInfo
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- CN103725424B CN103725424B CN201410032117.8A CN201410032117A CN103725424B CN 103725424 B CN103725424 B CN 103725424B CN 201410032117 A CN201410032117 A CN 201410032117A CN 103725424 B CN103725424 B CN 103725424B
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- catalytic distillation
- distillation tower
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention provides a kind of production method of biofuel, comprising: after being mixed with acid catalyst by grease inferior, obtain mixture; The top of described mixture by catalytic distillation tower is passed into, the bottom of alcohols material by catalytic distillation tower is passed into, be heated to alcohols material vaporization, grease inferior and the alcohols material after vaporizing react in catalytic distillation tower, collect the reaction effluent of board-like tower bottom, it is separated after removing catalyzer through separating device, and heating and pressurizing is reacted, and obtains biofuel crude product.Compared with prior art, the present invention is on each column plate, and the alcohols material of grease inferior, acid catalyst and vaporization constantly mass transfer and heat exchange occurs under through the airflow function of column plate, catalyzed reaction occurs simultaneously; Due to vapor liquid equilibrium effect, column plate is formed higher alcohol oil rate system, improve the transformation efficiency of reaction; The water-band of generation is gone out system by the steam simultaneously risen, and esterification is carried out to the degree of depth, reduces the acid number of reaction product.
Description
Technical field
The invention belongs to green, field of renewable energy technology, particularly relate to a kind of production method of biofuel.
Background technology
The renewable energy source that to take fatty acid methyl ester as the biofuel of feature be is raw material with plant or animal grease, due to its extremely low sulphur, nitrogen content, combustion processes is environmentally friendly, is therefore called as green energy resource.Because China is populous, needed for first grease will ensure that people live, government takes the industrial supporting policy not striving food with the people, therefore adopts not spendable waste grease such as the greases inferior such as hogwash fat, sewer oil, waste cooking oil to be that raw material production biofuel just seems significant.
Industrial employing waste grease is that the technology of raw material production biofuel is a lot, many employings vitriol oil is catalyzer, the Chinese patent being CN1382762A as publication number adopts sulfuric acid or Phenylsulfonic acid to be catalyzer, and publication number is that the Chinese patent of CN1412278A adopts sulfuric acid as catalyzer.The liquid acid catalysts such as sulfuric acid have corrodibility to equipment, and the acid-base neutralisation process of reaction product causes environmental pollution, are called as the disagreeableness production technique of environment.
In recent years, some adopt solid acid to be catalyzer thus the technology avoiding liquid acid to denounce also is suggested, the Chinese patent being CN1580190A as publication number proposes a kind of method utilizing solid acid to be catalyzer, adopts centrifugal method to remove solid catalyst, avoids the generation of sewage.The function of solid acid catalyst derives from the acid sites with catalytic activity that solid surface exists, and claim acid site, majority is oxide compound or the mixed oxide of non-transition element, and its catalytic performance is different from the oxide catalyst containing transition element.In addition, also having profit to carry type solid acid catalyst, liquid acid being carried on for being formed on solid carrier, as solid phosphoric acid catalyst.Although it is active that single component solid catalyst has good starting catalytic, single pass life is shorter, by the modification to support of the catalyst, the specific surface area making catalyzer can provide suitable, the acid site density that increases, sour type, increase antitoxin.Along with people to deepen continuously research to solid super-strong acid, catalyzer ability, improve physical strength etc.At present, the direction of study on the modification mainly contains: with metal oxide TiO
2for parent, add other metals or oxide compound, form multicomponent solid super-strong acid; Introduce rare-earth element modified; Introduce specific molecular sieve and nanosize metal oxide etc.
But, no matter be liquid acid or solid acid catalysis production biofuel, the problem of some general character of ubiquity: reaction times longer (being greater than 3h), product yield low (being less than 80%, not containing lighting end), reaction product acid number higher (being greater than 2mgKOH/g).Product acid number is higher means the national standard (< 0.8mgKOH/g) needing aftertreatment could meet biofuel, makes the production time of biofuel longer like this.
Publication number is the novel process that the Chinese patent of CN1775913A discloses a kind of preparing biodiesel from high acid value swill oil, its with the vitriol oil, strong phosphoric acid be catalyzer, stirring tank is for reactor, adopt the acidic substance such as alkaline wash method Removal of catalyst, 6 hours reaction times, reaction yield can reach 97.8%, and acid number is 3.0mgKOH/g.
Publication number is a kind of method that the Chinese patent of CN1580190A discloses solid acid, biofuel is prepared in base catalysis, and it is with ZrSO
4, SO
4 2-/ ZrO
2, HZSM
5for catalyzer, stirring tank are the technology of preparing of reactor, adopt centrifuging to remove solid catalyst, the reaction times is similarly 6h, and reaction yield is 99%.
Publication number is a kind of method that the Chinese patent of CN1810932A discloses middle temperature low-pressure process and prepares biofuel, with D72 solid acid be catalyzer, stirring tank is for reactor, adopt settling process to remove solid catalyst, alkaline wash method removes acidic substance, and the reaction times is 5h.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is the production method providing a kind of biofuel, and the method production time is shorter.
The invention provides a kind of production method of biofuel, comprise the following steps:
A) catalytic distillation Tower System is provided: described catalytic distillation Tower System comprises catalytic distillation tower and separating device; Described catalytic distillation tower is tray column; The column plate of described tray column is valve tray or sieve tray;
B), after being mixed with acid catalyst by grease inferior, mixture is obtained; The top of described mixture by catalytic distillation tower is passed into, the bottom of alcohols material by catalytic distillation tower is passed into, be heated to alcohols material vaporization, grease inferior and the alcohols material after vaporizing react in catalytic distillation tower, collect the reaction effluent of board-like tower bottom, obtain intermediate product; Described alcohols material is one or more in the straight-chain fatty alcohol of C1 ~ C6;
C) be separated after removing catalyzer through separating device by intermediate product, heating and pressurizing is reacted, and obtains biofuel crude product.
Preferably, described catalytic distillation Tower System also comprises compressor.
Preferably, described catalytic distillation Tower System also comprises reboiler.
Preferably, the column plate quantity of described tray column is 5 ~ 100 pieces.
Preferably, the percentage of open area of described column plate is 3 ~ 50%, and aperture is 2 ~ 100mm.
Preferably, the temperature of described tray column is 80 DEG C ~ 300 DEG C, and pressure is 0.1 ~ 5.0MPaG.
Preferably, the quality of described acid catalyst is 0.1% ~ 20% of oil quality inferior.
Preferably, the mass space velocity of described grease inferior in tray column is 0.05 ~ 2.0h
-1.
Preferably, the mol ratio of described grease inferior and alcohols material is 1:(3 ~ 24).
Preferably, described step C) in the temperature of reaction be 200 DEG C ~ 320 DEG C, the pressure of reaction is 4.0 ~ 20.0MPaG.
The invention provides a kind of production method of biofuel, comprising: catalytic distillation Tower System is provided: described catalytic distillation Tower System comprises catalytic distillation tower and separating device; Described catalytic distillation tower is tray column; The column plate of described tray column is valve tray or sieve tray; After being mixed with acid catalyst by grease inferior, obtain mixture; The top of described mixture by catalytic distillation tower is passed into, the bottom of alcohols material by catalytic distillation tower is passed into, be heated to alcohols material vaporization, grease inferior and the alcohols material after vaporizing react in catalytic distillation tower, collect the reaction effluent of board-like tower bottom, obtain intermediate product; Described alcohols material is one or more in the straight-chain fatty alcohol of C1 ~ C6; Be separated after removing catalyzer through separating device by intermediate product, heating and pressurizing is reacted, and obtains biofuel crude product.Compared with prior art, the present invention adopts the method for reaction mass continuously feeding, passed into by the top of tray column after grease inferior mixes with acid catalyst, and successively flow to bottom by column plate from top to bottom, alcohols material is passed into by the bottom of tray column, vaporize after being heated, successively flow to tower top by column plate from bottom to top, on each column plate, constantly there is mass transfer and heat exchange with the alcohols material of vaporization in grease inferior, acid catalyst, catalyzed reaction occurs under the airflow function passing column plate simultaneously; Due to vapor liquid equilibrium effect, the alcohols material concentration on column plate is higher, forms higher alcohol oil rate system, makes reaction to positive reaction future development, improves the transformation efficiency of reaction; Meanwhile, the water-band generated in reaction is gone out system by the steam of rising, esterification is carried out to the degree of depth, reduces the acid number of intermediate product; After intermediate product is separated removing catalyzer, heating and pressurizing makes reaction have good transesterify performance, thus the acid number of product can be made to reduce further.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 production biofuel schematic flow sheet.
Embodiment
The invention provides a kind of production method of biofuel, comprise the following steps:
A) catalytic distillation Tower System is provided: described catalytic distillation Tower System comprises catalytic distillation tower and separating device; Described catalytic distillation tower is tray column; The column plate of described tray column is valve tray or sieve tray;
B), after being mixed with acid catalyst by grease inferior, mixture is obtained; The top of described mixture by catalytic distillation tower is passed into, the bottom of alcohols material by catalytic distillation tower is passed into, be heated to alcohols material vaporization, grease inferior and the alcohols material after vaporizing react in catalytic distillation tower, collect the reaction effluent of board-like tower bottom, obtain intermediate product; Described alcohols material is one or more in the straight-chain fatty alcohol of C1 ~ C6;
C) be separated after removing catalyzer through separating device by intermediate product, heating and pressurizing is reacted, and obtains biofuel crude product.
The source of the present invention to all raw materials does not have special restriction, for commercially available.
Wherein, described catalytic distillation Tower System comprises tray column, and the column plate of described tray column is valve tray or sieve tray, is preferably sieve tray; The quantity of described column plate and structural parameter can be selected according to factors such as selecting the character of grease inferior, catalyst performance, and the quantity of described column plate is preferably 5 ~ 100 pieces, is more preferably 10 ~ 80 pieces, then are preferably 20 ~ 60 pieces; The height of weir of described tray column is preferably 30 ~ 200mm, is more preferably 50 ~ 150mm; The percentage of open area of described column plate is preferably 3% ~ 50%, is more preferably 10% ~ 40%, then is preferably 10% ~ 30%; The aperture of described column plate is preferably 2 ~ 100mm, is more preferably 5 ~ 80mm, is more preferably 5 ~ 60mm, then is preferably 5 ~ 40mm.
After being mixed with acid catalyst by grease inferior, obtain mixture; Wherein, described grease inferior is grease inferior well known to those skilled in the art, there is no special restriction, and being preferably acid number in the present invention is 10 ~ 180mgKOH/g, is more preferably 55 ~ 125mgKOH/g.
Described acid catalyst is acid catalyst alcoholysis to sound response effect well known to those skilled in the art, and there is no special restriction, can be solid acid catalyst, also can be liquid acid catalyst, the present invention is preferably solid acid catalyst; The particle diameter of described solid acid catalyst is preferably 0.1 ~ 3.0mm, can utilize grease viscosity inferior large feature that solid catalyst is not easily precipitated, can keep the requirement that solid-liquid is evenly distributed; Described solid acid catalyst be preferably in immobilized liquid acid catalyst, metal oxide-type catalyzer, sulfide-based catalyzer, metallic salt catalyzer, molecular sieve catalysts, heteropllyacids catalyzer and solid super strong acids catalyzer one or more; Described liquid acid catalyst is preferably ionic liquid acid catalyst.
Described immobilized liquid acid catalyst is preferably HF/Al
2o
3, BF
3/ Al
2o
3with H
3pO
4one or more in/diatomite; Described metal oxide-type catalyzer comprises simple oxide class catalyzer and composite oxides class catalyzer, is preferably Al
2o
3, SiO
2, B
2o
3, Nb
2o
5, Al
2o
3siO
2with Al
2o
3/ B
2o
3; Described molecular sieve catalysts comprises zeolite molecular sieve class catalyzer and non-zeolite molecular sieve class catalyzer, is preferably one or more in ZSM-5 zeolite, X zeolite, Y zeolite, B zeolite, mordenite, HZSM5 and ALPOSAPO; Described heteropolyacid is preferably H
3pW
12o
40, H
4siW
12o
40with H
3pMo
12o
40in one or more; Described solid super strong acids catalyzer comprises single-component solid super acids and the acid of polycomponent Composite super; Described single-component solid super acids be preferably in group VIII noble metals solid super-strong acid, ferric solid superacid, tin system solid super-strong acid and titanium system solid super-strong acid one or more, be more preferably SO
4 2-/ TiO
2, S
2o
8 2-/ TiO
2, SO
4 2-/ Fe
2o
3, SO
4 2-/ Fe
3o
4with Al
2o
3/ SO
4 2-in one or more; The acid of described polycomponent Composite super be preferably in other burning physical property solid super-strong acids of compound, magnetic coupling type solid acid catalyst, compound rare-earth element and linking agent carried superstrong solid acid and molecular sieve carried type solid super-strong acid one or more, be more preferably B
2o
3/ ZrO
2, Zr (SO
4)
2/ Fe
3o
4, add rare earth β-diketone complex
2o
3sO
4 2-/ Fe
3o
4sections based solid acid catalyst, SO
4 2-/ Ti
2la
2o, SO
4 2-/ TiO
2/ La
3+, SO
4 2-/ ZrO
2-Nd
2o
3, SO
4 2-/ ZrO
2-TiO
2/ La
3+, SO
4 2-/ TiO
2-MCM-41 and SO
4 2-/ ZrO
2one or more in-ZSM5.
In the present invention, described grease inferior and acid catalyst are preferably that 0.1% ~ 20% of oil quality inferior mixes according to the quality of catalyzer, obtain mixture, are more preferably 0.3% ~ 10%.
The top of described mixture by tray column is passed into, and successively flows to bottom by column plate from top to bottom; The bottom of alcohols material by tray column is passed into, vaporize after being heated, the steam of alcohols material successively flows to tower top by column plate from bottom to top, and grease inferior and the alcohols material after vaporizing react in tray column, collect the reaction effluent of board-like tower bottom, be intermediate product.In order to regulate the distribution of alcohols material in tray column, preferably at tower top entering part alcohols material; Its feed entrance point preferred arrangement is on first piece or second block of column plate, and when can make like this to prevent column plate more, the steam of alcohols material does not arrive top of tower timesharing, and the mixture of grease inferior and acid catalyst is divided by top of tower and flows at the bottom of tower.
Described alcohols material is one or more in the straight-chain fatty alcohol of C1 ~ C6 well known to those skilled in the art, there is no special restriction, is preferably methyl alcohol and/or ethanol in the present invention.
React after grease inferior and the alcohols material after gasifying carry out in tray column, in tray column of the present invention, the temperature of reaction is preferably 80 DEG C ~ 300 DEG C, is more preferably 100 DEG C ~ 200 DEG C; In tray column, the pressure of reaction is preferably 0.1 ~ 5.0MPaG, is more preferably 0.15 ~ 2.0MPaG; The mass space velocity of described grease inferior in tray column is preferably 0.05 ~ 2.0h
-1, be more preferably 0.25 ~ 1.0h
-1.
According to the present invention, described catalytic distillation tower optimum system choosing also comprises reboiler, and it to boil interchanger for tray column material again; Preferred employing shell and tube heat exchanger is as reboiler.Now, described alcohols material preferably passes into the bottom of tray column through reboiler, and contribute to reboiler and play heating properties, alcohols material is vaporized faster.
Described catalytic distillation optimum system choosing also comprises compressor, and it is a kind of gas boosting equipment, and the present invention more preferably selects roots blower, spiral-lobe compressor or centrifugal compressor as compressor.Alcohols material is heated after vaporization at the bottom of the tower of tray column, the steam of alcohols material successively flows to tower top by column plate from bottom to top, part overhead vapours can turn back on the bottom of tray column or the column plate of close bottom through compressor, preferably bottom tray column 1/1 to three/2nd position, the circulation of moisture content can be reduced like this, also can reduce the quantity that alcohols material reclaims simultaneously, the energy consumption of catalytic distillation system is reduced.
According to the present invention, the separating device in described catalytic distillation system is solid-liquid separating equipment or Phase separation equipment.
When acid catalyst used is solid acid catalyst, the reaction effluent bottom tray column makes product and solid acid catalyst be separated by solid-liquid separating equipment.Described solid-liquid separating equipment is preferably whizzer, filter or pressure filter, be more preferably filter, be preferably plate and frame filter, filer element type filter or leaf filter again, because the pressure and temp of reaction volume is all higher, adopt filter to be more favourable as solid-liquid Molecular Devices.
When described acid catalyst is liquid acid catalyst, the reaction overhead product bottom tray column is separated by Phase separation equipment.Described Phase separation equipment is preferably cyclone separator, butterfly centrifugal machine or liquid liquid settling vessel.
Isolate after catalyzer by intermediate product through separating device, heating and pressurizing is reacted, and wherein, the temperature of described reaction is preferably 200 DEG C ~ 320 DEG C, is more preferably 220 DEG C ~ 300 DEG C; The pressure of described reaction is preferably 4.0 ~ 20.0mPaG, is more preferably 4.0 ~ 9.0mPaG.
According to the present invention, this reaction is preferably carried out in high-temperature high-voltage reaction device.Described high-temperature high-voltage reaction device is high-temperature high-voltage reaction device well known to those skilled in the art, there is no special restriction, and it is a high pressure vessel, is built-in with grid distributor or particular fillers for improving fluid distribution.The length-to-diameter ratio of the device of high-temperature high-voltage reaction described in the present invention is preferably 5 ~ 100, is more preferably 20 ~ 80, then is preferably 20 ~ 50; In described high-temperature high-voltage reaction device, the quantity of built-in grid distributor or filler is preferably 1 ~ 20 group, is more preferably 1 ~ 10 group, then is preferably 1 ~ 5 group.
For reducing the time of reaction, described intermediate product after separating device removing catalyzer preferably high-pressure pump pressurization carry out heating then being delivered in high-temperature high-voltage reaction device with interchanger and react.Described high-pressure pump is high-pressure pump well known to those skilled in the art, there is no special restriction, and it is a kind of fluid pressurization handling equipment, is preferably high-speed pump or ram pump; Described interchanger is interchanger well known to those skilled in the art, there is no special restriction, and the intermediate product after removing catalyzer is warming up to the interchanger required for high-temperature high-voltage reaction by it, preferably adopts tube and shell heat exchanger.
In order to regulate the alcohol oil rate of the intermediate product after removing catalyzer, make it after heating and pressurizing, carry out transesterification reaction better, described intermediate product is separated removing catalyzer through separating device and preferably passes into the second alcohols material when heating and pressurizing is reacted, described second alcohols material is one or more in the straight-chain fatty alcohol of C1 ~ C6, be preferably methyl alcohol and/or ethanol, described second alcohols material can be identical with alcohols material, also can be different, there is no special restriction; Be preferably 6 ~ 32 according to the mol ratio of the intermediate product after the second alcohols material of the present invention and removing catalyzer, be more preferably 10 ~ 12.
After heating and pressurizing is reacted, obtain biofuel crude product.Described biofuel crude product preferably also carries out purification procedures, obtains biofuel.Described separating-purifying step is those skilled in the art's separating-purifying, there is no special restriction, and preferably adopt water washing to remove glycerine in the present invention, then heating removes light constituent, then the step of vacuum distilling collection overhead product carries out separating-purifying.
The present invention adopts the method for reaction mass continuously feeding, passed into by the top of tray column after grease inferior mixes with acid catalyst, and successively flow to bottom by column plate from top to bottom, alcohols material is passed into by the bottom of tray column, vaporize after being heated, successively flow to tower top by column plate from bottom to top, on each column plate, constantly there is mass transfer and heat exchange with the alcohols material of vaporization in grease inferior, acid catalyst, catalyzed reaction occurs under the airflow function passing column plate simultaneously; Due to vapor liquid equilibrium effect, the alcohols material concentration on column plate is higher, forms higher alcohol oil rate system, makes reaction to positive reaction future development, improves the transformation efficiency of reaction; Meanwhile, the water-band generated in reaction is gone out system by the steam of rising, esterification is carried out to the degree of depth, reduces the acid number of intermediate product; After intermediate product is separated removing catalyzer, heating and pressurizing makes reaction have good transesterify performance, thus the acid number of product can be made to reduce further.
In order to further illustrate the present invention, be described in detail below in conjunction with the production method of embodiment to a kind of biofuel provided by the invention.
In following examples, agents useful for same is commercially available: used catalyst is load sulfonic acid catalyst, and carrier is carclazyte.
Embodiment 1
Catalytic distillation system: the column plate of tray column is sieve tray, tower diameter
stage number is 30 pieces, height of weir 15mm, percentage of open area 13%; Tower top arrangement has grease opening for feed and methanol feeding mouth, arranges there is methanol feeding mouth at the bottom of tower; Every two-layer column plate arrangement has a liquid sampling mouth; Reboiler is electric heater; Shunting device is solid-liquid separating equipment.
High-temperature high-voltage reaction device: internal diameter
long 800mm, built-in 1 piece of fluid distributor, arranges there is a liquid phase thief hole in the middle part of reactor.
The cottonseed acid carburetion of acid number 118.41mgKOH/g is mixed with load sulfonic acid catalyst, catalyst levels is 8.75% of cottonseed acid carburetion quality, the inlet amount of cottonseed acid carburetion is 8.737mol/h, the inlet amount of fresh methanol is 35mol/h, the inlet amount of recycle methanol is 16mol/h, reaction pressure is 1.7MPaG, and tower top temperature is 163 DEG C, and column bottom temperature is 179 DEG C.First in tray column, be filled with methyl alcohol, heat up, pressurize, total reflux operation, to required pressure 1.7MPaG, stablizes methanol feeding amount, regulates tower top steam flow to make it pressure-stabilisation; Start High Temperature High Pressure methanol feeding and interchanger to heat up, regulate high-temperature high-voltage reaction device pressure to 7.5MPaG, temperature to 270 DEG C also makes it stable; Then grease and catalyst mixture charging is started, keep distillation tower stable operation, liquid level at the bottom of observing tower, adopt the liquid level at the bottom of mode stabilizer tower of interval blowing in OK range, after reaction 1h, blowing at the bottom of tower is sent to deep bed filter by self-pressure and removes solids, delivers to high-temperature heat-exchanging with high-pressure pump boosting, then enters high-temperature high-voltage reaction device, top discharge is reaction discharging, through pressure and temperature reducing
Glycerine is removed three times again with the distilled water wash of product quality 10% ~ 20%, then boil at ambient pressure to 130 DEG C again constant temperature 15min remove light constituent, vacuum distilling afterwards, collect overhead product, until reach 270 DEG C, keep 10min under 5mmHg vacuum, obtain biofuel.After tray column stable operation 24h, every 8 hours sampling analysis.
Fig. 1 is embodiment 1 production biofuel schematic flow sheet, wherein 1 is cottonseed acid carburetion, 2 is load sulfonic acid catalyst, 3 is fresh methanol, 4 is tower top methanol steam, 5 is the tower top methanol steam in order to reclaim, 6 is the tower top methanol steam circulated, 7 is circulation tower top methanol steam after compression, 8 for reacting discharging at the bottom of tower, 9 solid catalysts for filtering out, 10 is intermediate product, 11 is tray column (catalytic distillation tower), 12 is compressor, 13 is tower reactor pump, 14 is reboiler, 15 is solid-liquid separating equipment, 16 is methyl alcohol, 17 is high-pressure pump, 18 is high-temperature heat-exchanging, 19 is high-temperature high-voltage reaction product, 20 is high-temperature high-voltage reaction device.
From each column plate sampling analysis, analyze, analytical procedure to the biofuel obtained: reaction product compositional analysis adopts vapor-phase chromatography, other index analysis carry out with reference to biofuel national standard.Calculation of parameter: the biofuel obtained after vacuum distilling comprises fatty acid methyl ester, mono-glycerides, two sweet esters, glycerine, lipid acid, a small amount of component such as aldehyde ketone and hydro carbons, and each component concentration adopts area normalization method to calculate; Grease transformation efficiency (%)=[(100-removes the percentage composition of all lipid acid and triglyceride in the reaction product after light constituent)/100] × 100%; Biofuel yield (%)=(after vacuum fractions weight of oil/remove light constituent reaction product weight) × 100%; Column plate alcohol oil rate (mol/mol)=[in column plate sample, Methanol Molar is called the score and is counted/(in 1-column plate sample Methanol Molar percentage ratio)]; High-temperature high-voltage reaction alcohol oil rate (mol/mol)=[Methanol Molar percentage ratio in high temperature-pressure sample/(in 1-high temperature-pressure sample Methanol Molar percentage ratio)]; Device alcohol oil rate (mol/mol)=fresh methanol mole hour inlet amount/grease mole hour inlet amount.
Analytical results: column plate molar ratio of methanol to oil 35.39; High-temperature high-voltage reaction alcohol oil rate 12.2; Device molar ratio of methanol to oil 16.2; Grease transformation efficiency 99.9%; Biofuel yield 93.55%; Acid number of biodiesel 0.57mgKOH/g.
Embodiment 1 technological parameter and analytical results are in table 1.
Embodiment 2
Catalytic distillation system: the column plate of tray column is sieve tray, tower diameter
stage number is 30 pieces, height of weir 15mm, percentage of open area 13%; Tower top arrangement has grease opening for feed and methanol feeding mouth, arranges there is methanol feeding mouth at the bottom of tower; Every two-layer column plate arrangement has a liquid sampling mouth; Reboiler is electric heater; Shunting device is solid-liquid separating equipment.
High-temperature high-voltage reaction device: internal diameter
long 800mm, built-in 1 piece of fluid distributor, arranges there is a liquid phase thief hole in the middle part of reactor.
The rapic acid carburetion of acid number 123.37mgKOH/g is mixed with load sulfonic acid catalyst, catalyst levels is 5% of rapic acid carburetion quality, the inlet amount of rapic acid carburetion is 8.737mol/h, the inlet amount of fresh methanol is 35mol/h, the inlet amount of recycle methanol is 16mol/h, reaction pressure is 1.7MPaG, and tower top temperature is 163 DEG C, and column bottom temperature is 179 DEG C.First in tray column, be filled with methyl alcohol, heat up, pressurize, total reflux operation, to required pressure 1.7MPaG, stablizes methanol feeding amount, regulates tower top steam flow to make it pressure-stabilisation, start High Temperature High Pressure methanol feeding and interchanger to heat up, regulate high-temperature high-voltage reaction device pressure to 7.5MPaG, temperature to 270 DEG C also makes it stable, then grease and catalyst mixture charging is started, keep distillation tower stable operation, liquid level at the bottom of observing tower, adopt the liquid level at the bottom of mode stabilizer tower of interval blowing in OK range, after reaction 1h, blowing at the bottom of tower is sent to deep bed filter by self-pressure and removes solids, high-temperature heat-exchanging is delivered to high-pressure pump boosting, then high-temperature high-voltage reaction device is entered, top discharge is reaction discharging, glycerine is removed three times with the distilled water wash of product quality 10% ~ 20% again through pressure and temperature reducing, then boil at ambient pressure to 130 DEG C again constant temperature 15min remove light constituent, vacuum distilling afterwards, collect overhead product, until reach 270 DEG C, 10min is kept under 5mmHg vacuum, obtain biofuel.
Analytical procedure is with embodiment 1, and analytical results is: column plate alcohol oil rate 35.4; High-temperature high-voltage reaction alcohol oil rate 12.2; Device alcohol oil rate 16.2; Grease transformation efficiency 99.92%; Biofuel yield 94.01%; Acid number of biodiesel 0.93mgKOH/g.
Embodiment 2 technological parameter and analytical results are in table 1.
Embodiment 3
Catalytic distillation system: the column plate of tray column is sieve tray, tower diameter
stage number is 30 pieces, height of weir 15mm, percentage of open area 13%; Tower top arrangement has grease opening for feed and methanol feeding mouth, arranges there is methanol feeding mouth at the bottom of tower; Every two-layer column plate arrangement has a liquid sampling mouth; Reboiler is electric heater; Shunting device is solid-liquid separating equipment.
High-temperature high-voltage reaction device: internal diameter
long 800mm, built-in 1 piece of fluid distributor, arranges there is a liquid phase thief hole in the middle part of reactor.
The rapic acid carburetion of acid number 123.37mgKOH/g is mixed with load sulfonic acid catalyst, catalyst levels is 10% of rapic acid carburetion quality, the inlet amount of rapic acid carburetion is 8.737mol/h, the inlet amount of fresh methanol is 35mol/h, the inlet amount of recycle methanol is 16mol/h, reaction pressure is 1.7MPaG, and tower top temperature is 163 DEG C, and column bottom temperature is 179 DEG C.First in tray column, be filled with methyl alcohol, heat up, pressurize, total reflux operation, to required pressure 1.7MPaG, stablizes methanol feeding amount, regulates tower top steam flow to make it pressure-stabilisation, start High Temperature High Pressure methanol feeding and interchanger to heat up, regulate high-temperature high-voltage reaction device pressure to 7.5MPaG, temperature to 270 DEG C also makes it stable, then grease and catalyst mixture charging is started, keep distillation tower stable operation, liquid level at the bottom of observing tower, adopt the liquid level at the bottom of mode stabilizer tower of interval blowing in OK range, after reaction 1h, blowing at the bottom of tower is sent to deep bed filter by self-pressure and removes solids, high-temperature heat-exchanging is delivered to high-pressure pump boosting, then high-temperature high-voltage reaction device is entered, top discharge is reaction discharging, glycerine is removed three times with the distilled water wash of product quality 10% ~ 20% again through pressure and temperature reducing, then boil at ambient pressure to 130 DEG C again constant temperature 15min remove light constituent, vacuum distilling afterwards, collect overhead product, until reach 270 DEG C, 10min is kept under 5mmHg vacuum, obtain biofuel.
Analytical procedure is with embodiment 1, and analytical results is: column plate alcohol oil rate 35.4; High-temperature high-voltage reaction alcohol oil rate 12.2; Device alcohol oil rate 16.2; Grease transformation efficiency 99.95%; Biofuel yield 94.01%; Acid number of biodiesel 0.77mgKOH/g.
Embodiment 3 technological parameter and analytical results are in table 1.
Table 1 embodiment technological parameter and analytical results
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (3)
1. a production method for biofuel, is characterized in that, comprises the following steps:
A) catalytic distillation Tower System is provided: described catalytic distillation Tower System comprises catalytic distillation tower and separating device; Described catalytic distillation tower is tray column; The column plate of described tray column is valve tray or sieve tray; The column plate quantity of described tray column is 5 ~ 100 pieces; The height of weir of described tray column is 30 ~ 200mm; The percentage of open area of described column plate is 3 ~ 50%, and aperture is 2 ~ 100mm; The temperature of described tray column is 80 DEG C ~ 300 DEG C, and pressure is 0.1 ~ 5.0MPa;
B), after being mixed with acid catalyst by grease inferior, mixture is obtained; The top of described mixture by catalytic distillation tower is passed into, the bottom of alcohols material by catalytic distillation tower is passed into, be heated to alcohols material vaporization, grease inferior and the alcohols material after vaporizing react in catalytic distillation tower, collect the reaction effluent of board-like tower bottom, obtain intermediate product; Described alcohols material is one or more in the straight-chain fatty alcohol of C1 ~ C6;
The quality of described acid catalyst is 0.1% ~ 20% of oil quality inferior; The mass space velocity of described grease inferior in tray column is 0.05 ~ 2.0h
-1; The mol ratio of described grease inferior and alcohols material is 1:(3 ~ 24);
C) be separated after removing catalyzer through separating device by intermediate product, heating and pressurizing is reacted, and obtains biofuel crude product;
Described step C) in reaction temperature be 200 DEG C ~ 320 DEG C, the pressure of reaction is 4.0 ~ 20.0MPa.
2. production method according to claim 1, is characterized in that, described catalytic distillation Tower System also comprises compressor.
3. production method according to claim 1, is characterized in that, described catalytic distillation Tower System also comprises reboiler.
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| CN201410032117.8A CN103725424B (en) | 2014-01-23 | 2014-01-23 | A kind of production method of biofuel |
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| CN103031215B (en) * | 2013-02-18 | 2014-05-07 | 广西合众能源股份有限公司 | Continuous production device and method of biodiesel |
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