CN104707555A - Reactor and method for continuously preparing fatty acid ester by virtue of reactor - Google Patents
Reactor and method for continuously preparing fatty acid ester by virtue of reactor Download PDFInfo
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- CN104707555A CN104707555A CN201510074888.8A CN201510074888A CN104707555A CN 104707555 A CN104707555 A CN 104707555A CN 201510074888 A CN201510074888 A CN 201510074888A CN 104707555 A CN104707555 A CN 104707555A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0278—Feeding reactive fluids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/10—Ester interchange
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Abstract
The invention discloses a reactor and a method for continuously preparing fatty acid ester by virtue of the reactor, and relates to the field of biomass energy resources. The reactor comprises an oil-phase raw material container for containing raw oil, an alcohol-phase raw material container for containing alcohol, a packed column reactor for reacting the raw oil with alcohol and a product container for containing a product obtained by the reaction in the packed column reactor. The method comprises the following steps: 01, feeding the raw oil and a co-solvent into the oil-phase raw material container according to the mass ratio of raw oil to co-solvent being 1:(0.5-10), performing uniform mixing to obtain an oil phase, and feeding low-carbon alcohol into the alcohol-phase raw material container to obtain an alcohol phase; 02, adding a catalyst packing into column sections of the packed column reactor in a stacking or integral layering manner; 03, pumping the oil phase and the alcohol phase into the packed column reactor by virtue of a metering pump respectively, enabling the oil phase and the alcohol phase to contact in a parallel flow state, and performing transesterification reaction on the surface of the catalyst packing until the fatty acid ester content of a reaction product is stable; 04, extracting the reaction product from the column bottom, and demixing the reaction product to obtain a fatty acid ester phase and a reaction byproduct glycerin phase. According to the reactor and the method, solid alkali is taken as a packing and a catalyst; the method has the advantages of high reaction rate, no separation between the product and the catalyst and easiness in large-scale continuous production.
Description
Technical field
The present invention relates to biomass energy energy field, particularly relate to a kind of reactor and utilize the method for its continuous production fatty acid ester.
Background technology
Along with day by day reducing of world's non-renewable energy resources and day by day increasing the weight of of environmental pollution, the biodiesel that natural oil obtains through esterification or ester exchange can replace fossil class A fuel A, is a kind of environmental friendliness and reproducible green energy resource.Compared with the bio-fuel ethanol being all alternative fuel, China's production of biodiesel slower development.From China's refined oil demand, diesel oil is shorter relative to gasoline, and development biodiesel not only contributes to reducing Vehicular exhaust pollutant emission, also has the realistic meaning alleviating diesel oil shortage of resources.
Current biodiesel mainly occurs under the effect of catalyst with animal and plant fat and alcohol in reactor that ester exchange reaction obtains.Conventional method mainly contains chemical method, enzyme process and supercritical methanol technology.When adopting chemical method, because feedstock oil and alcohols do not dissolve each other, reaction is generally carried out in continuous stirred tank reactor, and stir mass transfer effect undesirable, the reaction time is long, and energy consumption is high, and the separating step of product and reactant is complicated, and technological process is long; Adopt enzyme process, low-carbon alcohols very easily causes biology enzyme poisoning and deactivation, and cause the service life of enzyme short, production cost is high; Adopt supercritical methanol technology, can inapplicable any catalyst, its limitation is that the temperature, pressure needed for reaction is too high.
CN101104812 adopts tubular reactor, achieve the continuous production of biodiesel in the supercritical state, the temperature of this reaction is 280 ~ 350 DEG C, required pressure is 16 ~ 50MPa, without the need to catalyst and the reaction time short, produce without discarded object, but this technique needs HTHP, high to equipment requirement, energy consumption is larger.
CN101284998A adopts fixed fat enzyme to be catalyst, and invented technique that a kind of catalytic reaction and separation process be coupled to prepare biodiesel, reaction condition gentleness, alcohol consumption is few, pollution-free, but the service life of enzyme is short, and the reaction time is long.
CN1916114A have employed tubular preheater, and tubular reactor achieves the continuous prodution of biodiesel, and adds cosolvent in reaction system.This invention substantially reduces the reaction time, reduces reaction temperature, not high to equipment requirement, but reacted after product can not be separated with catalyst.
CN1710026A adopts heterogeneous catalysis to achieve the continuous prodution of biodiesel, and product is separated with reactant.But this reaction temperature is up to 140 ~ 250 DEG C, and need to use a large amount of alcohol to take product out of reactor.
Summary of the invention
The present invention is directed to technique in prior art need HTHP, reaction time long, product and the problem such as catalyst can not be separated and propose a kind of reactor and utilize the method for this reactor continuous production fatty acid ester, in the present invention, solid base not only serves as filler but also serve as catalyst; It is fast that the method has reaction rate, without the need to carrying out being separated of product and catalyst, is easy to scale quantity-produced advantage.
Technical scheme of the present invention is as follows:
A kind of reactor, comprising the oil phase material container for filling feedstock oil, being used for filling the filler tower reactor that the alcohol phase material container of alcohol, feedstock oil and alcohol react and the product reservoir filled through the tower reactor reaction afterproduct of filler; There is opening at described filler tower reactor two ends, described oil phase material container is connected with the opening of filler tower reactor with one end respectively by pipeline with alcohol phase material container, described product reservoir is connected with filler tower reactor other end opening by pipeline, one end that one end that described filler tower reactor is connected with alcohol phase material container with oil phase material container is connected with product reservoir higher than filler tower reactor; Multiple tower joint is comprised in described filler tower reactor; The install pipeline that described oil phase material container is connected with filler tower reactor has metering control; The install pipeline that described alcohol phase material container is connected with filler tower reactor has metering control; The install pipeline that described oil phase material container is connected with filler tower reactor has safety control, and the install pipeline that alcohol phase material container is connected with filler tower reactor has safety control; The install pipeline that described product reservoir is connected with filler tower reactor has switching device.
Above-mentioned metering control is measuring pump.
Above-mentioned safety control is safety valve.
Above-mentioned switching device is for screwing valve.
Catalyst filling is filled with in above-mentioned filler tower reactor.
Utilize the method for above-mentioned reactor continuous production aliphatic acid, step is as follows:
S01: be 1: 0.5 ~ 10 drop in oil phase material container to mix and obtain oil phase in mass ratio by feedstock oil and cosolvent; Low-carbon alcohols is dropped in alcohol phase material container and obtain alcohol phase;
S02: by catalyst filling to huddle or the mode of whole block is added in the tower joint of filler tower reactor;
S03: respectively oil phase is pumped into filler tower reactor mutually with alcohol by measuring pump, oil phase and alcohol with and stream mode contact, carry out ester exchange reaction in filler catalyst surface and reach stable to product fatty acid ester content;
S04: product from extraction at the bottom of tower, after layering fatty acid ester phase and byproduct of reaction glycerine phase.
Above-mentioned raw materials oil is one or more in soybean oil, rapeseed oil, palm oil, cottonseed oil, algal oil, coptis seed oil, corn oil, rubber seed oil, smooth bark seeds of trees oil, sunflower oil.
Above-mentioned cosolvent is one or more in benzinum, oxolane, hexane, propane, pentane, butanone, Isosorbide-5-Nitrae one dioxane.
Above-mentioned low-carbon alcohols is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isobutanol.
Above-mentioned catalyst filling is by solid base Na
2siO
39H
2o combines with shaping filler and in 100 ~ 500 DEG C of Muffle furnaces, calcines 1 ~ 4h and obtains Na
2siO
3attachment filler.
Above-mentioned shaping filler is Sita ring, Pall ring, Raschig ring or gauze packing.
Above-mentioned catalyst filling in the preparation, can mix base catalyst CaO, MgO, Mg (OH)
2, Al
2o
3, TiO
2in one or more jointly calcine.
Above-mentioned Oil phase flow rate controls at 1 ~ 20mL/min, and alcohol phase flow control is at 0.5 ~ 5mL/min.
Above-mentioned oil phase and alcohol are 20 ~ 60 DEG C in the tower reactor reaction temperature of filler, and the reaction time is 40 ~ 180min.
Beneficial effect of the present invention:
(1) the present invention utilizes packed tower reactor to prepare biodiesel, and use heterogeneous catalysis, being combined with filler by catalyst of innovation, makes it in packed tower reactor, not only serve as filler but also serve as catalyst, achieves being separated of reactant and product.
(2) cosolvent add the viscosity reducing oil phase, add oil phase and alcohol mutually between mass transfer, drive oil phase to show vigorous reaction occurs at catalyst filling with alcohol.
(3) the present invention is a kind of technique of continuous production fatty acid ester, in course of reaction, the fatty acid ester generated shifts out in time, along with shifting out of product, reversible ester exchange reaction balance moves to product one end, accelerate reaction rate, shorten the reaction time, product fatty acid ester yield is high.
Accompanying drawing explanation
Fig. 1 is the structural representation of reactor of the present invention.
Detailed description of the invention
In order to better the present invention is described, be now further described by reference to the accompanying drawings.
Be illustrated in figure 1 reactor of the present invention, comprise the filler tower reactor 4 reacted for the oil phase material container 1 of dress feedstock oil, the alcohol phase material container 2 being used for filling alcohol, feedstock oil and alcohol and the product reservoir 3 filled through the tower reactor reaction afterproduct of filler; There is opening at filler tower reactor 4 two ends, described oil phase material container 1 is connected with the opening 5 of filler tower reactor 5 with one end respectively by pipeline with alcohol phase material container 3, described product reservoir 3 is connected with filler tower reactor 4 other end opening 6 by pipeline, one end that one end that filler tower reactor 4 is connected with alcohol phase material container 2 with oil phase material container 1 is connected with product reservoir 3 higher than filler tower reactor 4; Multiple tower joint 10 is comprised in described filler tower reactor 4; The install pipeline that oil phase material container 1 is connected with filler tower reactor 4 has metering control 7, and the install pipeline that alcohol phase material container is connected with filler tower reactor has metering control; Metering control 7 is measuring pump; The install pipeline that oil phase material container 1 is connected with filler tower reactor 4 has safety control 8, and the install pipeline that alcohol phase material container 2 is connected with filler tower reactor 4 has safety control 8, and safety control 8 is safety valve; The install pipeline that product reservoir 3 is connected with filler tower reactor 4 has switching device 9, and switching device 9 is for screwing valve; Catalyst filling is filled with in filler tower reactor 4.
Embodiment 1:
Feedstock oil selects soybean oil, cosolvent to select benzinum (boiling range 60 ~ 90 DEG C), and alcohol selects methyl alcohol mutually, and preformed catalyst selects the Sita ring of 3mm*3mm, and filling mode is for huddling.
By solid base Na
2siO
39H
2o burns to melting in 60 ~ 65 DEG C, then is attached on the Sita ring of 3mm*3mm by this melt substance, and in Muffle furnace, 400 DEG C of calcining 2h make Na
2siO
3the ring-like attachment filler of-Sita.Na is loaded in tower
2siO
3the ring-like attachment filler of-Sita.500g soybean oil and 250g benzinum (boiling range 60 ~ 90 DEG C) are mixed in oil phase material container, 80g methyl alcohol loads alcohol phase material container.Open measuring pump, by tower top charging.Control Oil phase flow rate is 3mL/min, alcohol phase flow velocity 0.5mL/min, and flows to material, extraction at the bottom of tower, reaction temperature 45 DEG C.After 120min, collect tower reactor discharging, carry out separatory.Carry out decompression distillation to separatory gained oil phase mutually with alcohol, oil phase obtains product fatty acid esters, benzinum recycling capable of circulation, and alcohol obtains glycerine and methyl alcohol mutually, and methanol loop recycles.Through gas chromatographic analysis, obtain fatty acid ester yield 85.3%.
Embodiment 2:
Feedstock oil selects rapeseed oil, cosolvent to select benzinum (boiling range 60 ~ 90 DEG C), and alcohol selects methyl alcohol mutually, and preformed catalyst selects the Pall ring of 3mm*3mm, and filling mode is whole block.
By solid base Na
2siO
39H
2o burns to melting in 60 ~ 65 DEG C, then is attached on the Pall ring of 3mm*3mm by this melt substance, and in Muffle furnace, 200 DEG C of calcining 4h make Na
2siO
3the ring-like attachment filler of-Bauer.Na is loaded in tower
2siO
3the ring-like attachment filler of-Bauer.500g rapeseed oil and 500g benzinum (boiling range 60 ~ 90 DEG C) are mixed in oil phase material container, 200g methyl alcohol loads alcohol phase material container.Open measuring pump, by tower top charging.Control Oil phase flow rate is 5mL/min, alcohol phase flow velocity 1mL/min, and flows to material, extraction at the bottom of tower, reaction temperature 60 DEG C.After 75min, collect tower reactor discharging, carry out separatory.Carry out decompression distillation to separatory gained oil phase mutually with alcohol, oil phase obtains product fatty acid esters, benzinum recycling capable of circulation, and alcohol obtains glycerine and methyl alcohol mutually, and methanol loop recycles.Through gas chromatographic analysis, obtain fatty acid ester yield 96.7%.
Embodiment 3:
Feedstock oil selects palm oil, cosolvent to select oxolane, and alcohol selects methyl alcohol mutually, and preformed catalyst selects small-sized gauze packing, and filling mode is for huddling.
By solid base Na
2siO
39H
2o burns to melting in 60 ~ 65 DEG C, adds 2gMgO powder, then is attached on small-sized gauze packing by this molten mixture, and in Muffle furnace, 200 DEG C of calcining 3h make Na
2siO
3-MgO-net ring type attachment filler.Na is loaded in tower
2siO
3-MgO-net ring type attachment filler.360g palm oil and 720g oxolane are mixed in oil phase material container, 500g methyl alcohol loads alcohol phase material container.Open measuring pump, by tower top charging.Control Oil phase flow rate is 8mL/min, alcohol phase flow velocity 1.5mL/min, and flows to material, extraction at the bottom of tower, reaction temperature 40 DEG C.After 50min, collect tower reactor discharging, carry out separatory.Carry out decompression distillation to separatory gained oil phase mutually with alcohol, oil phase obtains product fatty acid esters, oxolane recycling capable of circulation, and alcohol obtains glycerine and methyl alcohol mutually, and methanol loop recycles.Through gas chromatographic analysis, obtain fatty acid ester yield 98.2%.
Embodiment 4:
Feedstock oil selects cottonseed, cosolvent to select n-hexane, and alcohol selects ethanol mutually, and preformed catalyst selects small-sized Raschig ring, and filling mode is for huddling.
By solid base Na
2siO
39H
2o burns to melting in 60 ~ 65 DEG C, adds 1.6gCaO powder, then is attached on small-sized Raschig ring by this molten mixture, and in Muffle furnace, 400 DEG C of calcining 1h make Na
2siO
3-CaO-Raschig ring type attachment filler.Na is loaded in tower
2siO
3-CaO-Raschig ring type attachment filler.362g cottonseed oil and 1086g n-hexane are mixed in oil phase material container, 256g ethanol loads alcohol phase material container.Open measuring pump, by tower top charging.Control Oil phase flow rate is 12mL/min, alcohol phase flow velocity 1mL/min, and flows to material, extraction at the bottom of tower, reaction temperature 25 DEG C.After 60min, collect tower reactor discharging, carry out separatory.Carry out decompression distillation to separatory gained oil phase mutually with alcohol, oil phase obtains product fatty acid esters, n-hexane recycling capable of circulation, and alcohol obtains glycerine and ethanol mutually, ethanol cycling and reutilization.Through gas chromatographic analysis, obtain fatty acid ester yield 92.3%
Embodiment 5:
Feedstock oil selects algal oil, cosolvent to select propane, and alcohol selects ethanol mutually, and preformed catalyst selects the Sita ring of 3mm*3mm, and filling mode is for huddling.
By solid base Na
2siO
39H
2o burns to melting in 60 ~ 65 DEG C, then is attached on the Sita ring of 3mm*3mm by this melt substance, and in Muffle furnace, 300 DEG C of calcining 3h make Na
2siO
3the ring-like attachment filler of-Sita.Na is loaded in tower
2siO
3the ring-like attachment filler of-Sita.362g algal oil and 1810g propane are mixed in oil phase material container, 896g ethanol alcohol loads alcohol phase material container.Open measuring pump, by tower top charging.Control Oil phase flow rate is 15mL/min, alcohol phase flow velocity 2mL/min, and flows to material, extraction at the bottom of tower, reaction temperature 50 (DEG C.After 45min, collect tower reactor discharging, carry out separatory.Carry out decompression distillation to separatory gained oil phase mutually with alcohol, oil phase obtains product fatty acid esters, propane recycling capable of circulation, and alcohol obtains glycerine and ethanol mutually, ethanol cycling and reutilization.Through gas chromatographic analysis, obtain fatty acid ester yield 94.6%
Embodiment 6:
Feedstock oil selects Seed Oil of Pistacia Bunge, cosolvent to select pentane, and alcohol selects butanols mutually, and preformed catalyst selects the Sita ring of 3mm*3mm, and filling mode is whole block.
By solid base Na
2siO
39H
2o burns to melting in 60 ~ 65 DEG C, adds 2.4gMg (OH)
2powder, then this molten mixture is attached on the Sita ring of 3mm*3mm, in Muffle furnace, 100 DEG C of calcining 4h make Na
2siO
3-Mg (OH)
2the ring-like attachment filler of-Sita.Na is loaded in tower
2siO
3-Mg (OH)
2the ring-like attachment filler of-Sita.362g Seed Oil of Pistacia Bunge and 2896g pentane are mixed in oil phase material container, 2130g butanols loads alcohol phase material container.Open measuring pump, by tower top charging.Control Oil phase flow rate is 20mL/min, alcohol phase flow velocity 5mL/min, and flows to material, extraction at the bottom of tower, reaction temperature 60 DEG C.After 55min, collect tower reactor discharging, carry out separatory.Carry out decompression distillation to separatory gained oil phase mutually with alcohol, oil phase obtains product fatty acid esters, pentane recycling capable of circulation, and alcohol obtains glycerine and butanols mutually, butanols cycling and reutilization.Through gas chromatographic analysis, obtain fatty acid ester yield 88.7%.
Embodiment 7:
Feedstock oil selects corn oil, cosolvent to select butanone, and alcohol selects isopropyl alcohol mutually, and preformed catalyst selects small-sized Raschig ring, and filling mode is whole block.
By solid base Na
2siO
39H
2o burns to melting in 60 ~ 65 DEG C, adds 1.2gMgO powder, then is attached on small-sized Raschig ring by this molten mixture, and in Muffle furnace, 100 DEG C of calcining 4h make Na
2siO
3-MgO-Raschig ring type attachment filler.Na is loaded in tower
2siO
3-MgO-Raschig ring type attachment filler.181g corn oil and 1810g butanone are mixed in oil phase material container, 304g isopropyl alcohol loads alcohol phase material container.Open measuring pump, by tower top charging.Control Oil phase flow rate is 14mL/min, alcohol phase flow velocity 3mL/min, and flows to material, extraction at the bottom of tower, reaction temperature 60 DEG C.After 80min, collect tower reactor discharging, carry out separatory.Carry out decompression distillation to separatory gained oil phase mutually with alcohol, oil phase obtains product fatty acid esters, butanone recycling capable of circulation, and alcohol obtains glycerine and isopropyl alcohol mutually, isopropyl alcohol cycling and reutilization.Through gas chromatographic analysis, obtain fatty acid ester yield 84.6%.
Embodiment 8:
Feedstock oil selects rubber seed oil, cosolvent to select Isosorbide-5-Nitrae-dioxane, and mixed alcohol (isobutanol and methyl alcohol) selected mutually by alcohol, and preformed catalyst selects the Pall ring of 3mm*3mm, and filling mode is for huddling.
By solid base Na
2siO
39H
2o burns to melting in 60 ~ 65 DEG C, then is attached on the Pall ring of 3mm*3mm by this melt substance, and in Muffle furnace, 400 DEG C of calcining 2h make Na
2siO
3the ring-like attachment filler of-Bauer.Na is loaded in tower
2siO
3the ring-like attachment filler of-Bauer.181g rubber seed oil and 724g1,4-dioxane are mixed in oil phase material container, 100g isobutanol and 50g methyl alcohol mix in alcohol phase material container.Open measuring pump, by tower top charging.Control Oil phase flow rate is 2.8mL/min, alcohol phase flow velocity 0.7mL/min, and flows to material, extraction at the bottom of tower, reaction temperature 55 DEG C.After 40min, collect tower reactor discharging, carry out separatory.Carry out decompression distillation to separatory gained oil phase mutually with alcohol, oil phase obtains product fatty acid esters, Isosorbide-5-Nitrae-dioxane recycling capable of circulation, and alcohol obtains glycerine, isobutanol and methyl alcohol mutually, isobutanol and methanol loop recycling.Through gas chromatographic analysis, obtain fatty acid ester yield 88.2%.
Embodiment 9:
Smooth bark seeds of trees oil selected by feedstock oil, benzinum (boiling range 30 ~ 60 DEG C) selected by cosolvent, and alcohol selects propyl alcohol mutually, and preformed catalyst selects small-sized gauze packing, and filling mode is for huddling.
By solid base Na2SiO
39H
2o burns to melting in 60 ~ 65 DEG C, adds 1.2gMgO powder, then is attached to by this molten mixture on small-sized netted packing ring, and in Muffle furnace, 300 DEG C of calcining 4h make Na
2siO
3-MgO-net ring type attachment filler.Na2SiO is loaded in tower
3-MgO-net ring type attachment filler.362g smooth bark seeds of trees oil and 1086g benzinum (boiling range 30 ~ 60 DEG C) are mixed in oil phase material container, 197g propyl alcohol loads in alcohol phase material container.Open measuring pump, by tower top charging.Control Oil phase flow rate is 4.8mL/min, alcohol phase flow velocity 0.6mL/min, and flows to material, extraction at the bottom of tower, reaction temperature 20 DEG C.After 75min, collect tower reactor discharging, carry out separatory.Carry out decompression distillation to separatory gained oil phase mutually with alcohol, oil phase obtains product fatty acid esters, benzinum (boiling range 30 ~ 60 DEG C) recycling capable of circulation, and alcohol obtains glycerine and propyl alcohol mutually, propyl alcohol cycling and reutilization.Through gas chromatographic analysis, obtain fatty acid ester yield 87.3%.
Embodiment 10:
Feedstock oil selects sunflower oil, cosolvent to select benzinum (boiling range 60 ~ 90 DEG C), and mixed alcohol (methyl alcohol and propyl alcohol) selected mutually by alcohol, and preformed catalyst selects small-sized Raschig ring filler, and filling mode is whole block.
By solid base Na
2siO
39H
2o burns to melting in 60 ~ 65 DEG C, then is attached to by this melt substance on small-sized Raschig ring filler ring, and in Muffle furnace, 500 DEG C of calcining 2h make Na
2siO
3-Raschig ring type attachment filler.Na is loaded in tower
2siO
3-Raschig ring type attachment filler.362g soybean oil and 3620g benzinum (boiling range 60 ~ 90 DEG C) are mixed in oil phase material container, 1448g methyl alcohol loads in alcohol phase material container.Open measuring pump, by tower top charging.Control Oil phase flow rate is 10mL/min, alcohol phase flow velocity 5mL/min, and flows to material, extraction at the bottom of tower, reaction temperature 60 DEG C.After 180min, collect tower reactor discharging, carry out separatory.Carry out decompression distillation to separatory gained oil phase mutually with alcohol, oil phase obtains product fatty acid esters, benzinum (boiling range 60 ~ 90 DEG C) recycling capable of circulation, and alcohol obtains methyl alcohol and propyl alcohol mutually, recycling capable of circulation.Through gas chromatographic analysis, obtain fatty acid ester yield 96.8%.
Claims (10)
1. a reactor, is characterized in that: comprising the oil phase material container for filling feedstock oil, being used for filling the filler tower reactor that the alcohol phase material container of alcohol, feedstock oil and alcohol react and the product reservoir filled through the tower reactor reaction afterproduct of filler; There is opening at described filler tower reactor two ends, described oil phase material container is connected with the opening of filler tower reactor with one end respectively by pipeline with alcohol phase material container, described product reservoir is connected with filler tower reactor other end opening by pipeline, one end that one end that described filler tower reactor is connected with alcohol phase material container with oil phase material container is connected with product reservoir higher than filler tower reactor; Multiple tower joint is comprised in described filler tower reactor; The install pipeline that described oil phase material container is connected with filler tower reactor has metering control; The install pipeline that described alcohol phase material container is connected with filler tower reactor has metering control; The install pipeline that described oil phase material container is connected with filler tower reactor has safety control, and the install pipeline that described alcohol phase material container is connected with filler tower reactor has safety control; The install pipeline that described product reservoir is connected with filler tower reactor has switching device; Described metering control is measuring pump, and described safety control is safety valve, and described switching device, for screwing valve, is filled with catalyst filling in described filler tower reactor.
2. utilize the method for reactor continuous production aliphatic acid described in claim 1, it is characterized in that: step is as follows:
S01: be 1: 0.5 ~ 10 drop in oil phase material container to mix and obtain oil phase in mass ratio by feedstock oil and cosolvent; Low-carbon alcohols is dropped in alcohol phase material container and obtain alcohol phase;
S02: by catalyst filling to huddle or the mode of whole block is added in the tower joint of filler tower reactor;
S03: respectively oil phase is pumped into filler tower reactor mutually with alcohol by measuring pump, oil phase and alcohol with and stream mode contact, carry out ester exchange reaction in filler catalyst surface and reach stable to product fatty acid ester content;
S04: product from extraction at the bottom of tower, after layering fatty acid ester phase and byproduct of reaction glycerine phase.
3. the method for continuous production aliphatic acid according to claim 6, is characterized in that: described feedstock oil is one or more in soybean oil, rapeseed oil, palm oil, cottonseed oil, algal oil, coptis seed oil, corn oil, rubber seed oil, smooth bark seeds of trees oil, sunflower oil.
4. the method for continuous production aliphatic acid according to claim 6, is characterized in that: described cosolvent is one or more in benzinum, oxolane, hexane, propane, pentane, butanone, Isosorbide-5-Nitrae-dioxane.
5. the method for continuous production aliphatic acid according to claim 6, is characterized in that: described low-carbon alcohols is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isobutanol.
6. the method for continuous production aliphatic acid according to claim 6, is characterized in that: described catalyst filling is for by solid base Na
2siO
39H
2o combines with shaping filler and in 100 ~ 500 DEG C of Muffle furnaces, calcines 1 ~ 4h and obtains Na
2siO
3attachment filler.
7. the method for continuous production aliphatic acid according to claim 10, is characterized in that: described shaping filler is Sita ring, Pall ring, Raschig ring or gauze packing.
8. the method for continuous production aliphatic acid according to claim 2, is characterized in that: described catalyst filling in the preparation, can mix base catalyst CaO, MgO, Mg (OH)
2, Al
2o
3, TiO
2in one or more jointly calcine.
9. the method for continuous production aliphatic acid according to claim 2, it is characterized in that: described Oil phase flow rate controls at 1 ~ 20mL/min, alcohol phase flow control is at 0.5 ~ 5mL/min.
10. the method for continuous production aliphatic acid according to claim 2, is characterized in that: described oil phase and alcohol are 20 ~ 60 DEG C in the tower reactor reaction temperature of filler, and the reaction time is 40 ~ 180min.
Priority Applications (1)
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|---|---|---|---|
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| CN112427002A (en) * | 2020-11-21 | 2021-03-02 | 贵州锦江生物能源科技有限公司 | Tower-type superfine contact reaction device for biodiesel |
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