CN101235351B - Fixed enzyme membrane reactor, preparation thereof and method for producing biological diesel oil by the same - Google Patents
Fixed enzyme membrane reactor, preparation thereof and method for producing biological diesel oil by the same Download PDFInfo
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- CN101235351B CN101235351B CN2008100597765A CN200810059776A CN101235351B CN 101235351 B CN101235351 B CN 101235351B CN 2008100597765 A CN2008100597765 A CN 2008100597765A CN 200810059776 A CN200810059776 A CN 200810059776A CN 101235351 B CN101235351 B CN 101235351B
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Abstract
The invention relates to an immobilized enzyme membrane reactor and the preparation thereof and a method for producing bio-diesel. The method comprises filling superfine fiber complex film in a die whose inside and outside are double cylindrical shape to form a film reactor, injecting activating agent solution and lipase solution in the film reactor in turn through adopting a cross-flow filtration mode, leading lipase to be chemically fixed on superfine fiber membrane surface, getting an enzyme membrane reactor which is fixed with lipase, respectively injecting mixed solution of animal and vegetable oil and carbinol in the inner side and the outer side of the superfine fiber complex film, doing catalytic alcoholysis reaction on fiber membrane surface, and producing bio-diesel. The enzyme gathering catalysis of the method of the invention is integral with a membrane separation process, and the method of the invention simplifies manufacturing technique, and meanwhile, the method of the invention overcomes inhabitation of lower alcohol to enzymatic activity in the process of catalyzing, the immobilized enzyme membrane reactor can be repeatedly used, which can achieve continuous production, improves production efficiency, and has excellent industrial application prospect.
Description
Technical field
The invention belongs to fixed enzyme membrane reactor and preparation utilisation technology thereof, be specifically related to a kind of fixed enzyme membrane reactor production method of bio-diesel oil.
Background technology
Along with the exhaustion day by day of petroleum resources and the enhancing of public's environmental consciousness, reproducible environmental type fuel---biofuel has caused the extensive concern of countries in the world.Biofuel is the energy that a kind of character of from reproducible biomass resource, obtaining is similar to petroleum diesel, and its staple is ester classes such as formed methyl esters of longer chain fatty acid or ethyl ester.Compare with petroleum diesel, biofuel has close combustionproperty, and biofuel is far smaller than petroleum diesel to the corrodibility of mover; Biofuel does not contain aromatic hydrocarbon and sulphur content is extremely low, can significantly reduce the discharging of pollutent, and biofuel is a raw material with the animal-plant oil simultaneously, has recyclability.
At present, adopting the most in the world, the production of biodiesel technology is the ester exchange process of base catalysis.Adopt alkali as catalyzer, raw material must be refining through strictness, and a spot of free-water or lipid acid all can influence the catalytic activity of catalyzer.There are shortcomings such as flow process is complicated, pure consumption is big, energy consumption is big, environmental pollution is big in this technology simultaneously.In order to overcome above shortcoming, each state was all in the exploitation of being devoted to the biofuel new production process in the last few years.Lipase-catalyzed transesterify biodiesel synthesis has advantages such as reaction conditions gentleness, technology is simple, environmental pollution is little, receives people's attention day by day.CN1436834 is acyl acceptor with the short-chain aliphatic ester, under suitable TR, utilize renewable resources production biofuel such as biological enzyme animal-plant oil.CN1640991 will pass through the raw material animal-plant oil of filtration and emulsifying, add methyl alcohol or ethanol, in encloses container, utilize immobilized lipase catalyzed transesterification on the organic solvent oil-water interface.CN1818026 is deposited in the ball shape fixation enzyme in the packed bed enzyme column type reactor with state of nature, utilizes this packed bed enzyme column type reactor in non-aqueous system catalyzed alcoholysis animal-plant oil production biofuel.European patent EP 1705238 as reaction medium, is utilized lipase-catalyzed animal-plant oil alcoholysis production biofuel with organic hydrophilic solvent.U.S. Pat 6398707 adopts immobilized lipase zymotechnic catalysis animal-plant oil alcoholysis production biofuel, has overcome the disadvantageous effect of low-carbon alcohol to lipase activity.Utilize lipase-catalyzed biodiesel synthesis more and more to draw attention, but the zymin fancy price, and immobilized enzyme is difficult to from reaction system, reclaim repeated use on free enzyme or the microballoon class carrier, makes it increase production cost; In addition; Required packed bed enzyme column type reactor catalyzed alcoholysis animal-plant oil in non-aqueous system; There is restraining effect and the substrate diffusional resistance of organic solvent, make the easy inactivation of enzyme and reduce catalytic efficiency (, can't realize the real-time separation of hydrolysate etc. simultaneously lipase activity.These problems have all seriously hindered the industrialized paces of enzyme process biodiesel synthesis.
Prior art has utilized electrostatic spinning technique to prepare to have high-specific surface area, high voidage and the fabulous connective superfine fibrous membrane materials in hole; Use it for enzyme immobilization, can effectively improve the catalytic efficiency (of the enzyme amount of carrying, the diffusion control when eliminating enzymic catalytic reaction and the raising immobilized enzyme of immobilized enzyme.But also do not utilize ultra-fine fibre membrane prepare fixed enzyme membrane reactor at present, and be used for the technology of hydrolysis animal-plant oil production biofuel.So; Being necessary to develop a kind of is mould material with the ultra-fine fibre with high-specific surface area and high voidage; Make up fixed enzyme membrane reactor, effectively improve the catalytic efficiency (of the enzyme amount of carrying, the diffusion control when eliminating enzymic catalytic reaction and the raising immobilized enzyme of immobilized enzyme; Simultaneously, this fixed enzyme membrane reactor is used for hydrolysis animal-plant oil production biofuel, realization response catalysis synchronously and product separation function reduce production costs, and simplify production technique, enhance productivity.
Summary of the invention
The object of the invention will use ultra-fine fibre to be mould material exactly, makes up a kind of fixed enzyme membrane reactor, and uses it for the production biofuel; Realization response catalysis synchronously and product separation function; Reduce production costs, and simplify production technique, enhance productivity.
Be the technical scheme that realizes that above-mentioned purpose is taked:
One, the constructional feature of fixed enzyme membrane reactor of the present invention is to use the ultra-fine fibre composite package of Fibre diameter as 30-1000nm; With the polyester non-woven fabric is propping material; Double cylinder-shaped film reaction device inside and outside the formation; Inboard and the film reaction device film outside of film reaction device film is wherein arranged, and the inboard fiber surface of film is activated and enzyme immobilization; 3 film reaction devices are concatenated into one, two, three enzyme mebrane reactor.
Two, the method for this kind fixed enzyme membrane reactor preparation comprises following process step:
(1) vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/Rocryl 400 or vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer are dissolved in are made into spinning solution in the solvent and carry out electrostatic spinning and process the ultra-fine fibre composite package; With the polyester non-woven fabric is propping material; It is loaded in inside and outside double cylinder-shaped film tool, form one, two, three enzyme mebrane reactor of 3 film tool polyphones of membrane module formation.
Described vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/Rocryl 400 or vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer, multipolymer viscosity-average molecular weight (M η) is 5～200,000; 2-methacryloxypropyl-ethyl in the multipolymer-phosphatidylcholine mole percent level is 1～15%, and Rocryl 400 (or aminoethyl methacrylate) mole percent level is 1～15%.
Described solvent is a kind of or more multiple than blended with arbitrarily in DMSO 99.8MIN., N or the N,N-DIMETHYLACETAMIDE;
Described electrostatic spinning voltage is that 5kV～15kV, spinning nozzle solution flow are that 0.1mL/h～2.0mL/h, receiving range are 5cm～25cm.
The ultra-fine fibre composite package is to be that the ultra-fine fibre of 30～1000 nanometers compiles and forms by diameter.
(2) adopt the mode of cross flow filter earlier epoxy chloropropane or LUTARALDEHYDE to be circulated in membrane reactor device under 20～30 ℃ 1～3 hour, again lipase solution was circulated in membrane reactor device under 20～30 ℃ 1～3 hour; Epoxy chloropropane or LUTARALDEHYDE and lipase solution all get into film inner layer via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor.
Described lipase solution is that lypase is dissolved in the pH value is to process in 7.0 the phosphate buffer soln;
Three, the invention provides described fixed enzyme membrane reactor and be used for the production method of bio-diesel oil: will be through filtering the animal-plant oil mixing solutions of handling; Inject enzyme membrane device tunica fibrosa inboard 4. with certain flow rate, 5. inject methyl alcohol in the enzyme membrane device tunica fibrosa outside simultaneously.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates.
Described animal-plant oil mixing solutions is that 70～80% animal-plant oil and mass ratio are the mixing solutions that 20～30% ordinary diesel oil are formed by mass ratio.
The flow velocity of described animal-plant oil mixing solutions and methyl alcohol is 0.1～5L/h.
Compared with prior art, advantage of the present invention is:
(1) containing the reactive group superfine fibre film can be through the immobilization of chemical covalent method reality enzyme, and zymoprotein and carrier are not easy desorption through covalent bonds.
(2) used electrostatic spinning ultra-fine fibre composite package has high specific surface area and voidage, can significantly improve the enzyme amount of carrying of immobilized enzyme, and helps the diffusion of substrate, improves the catalytic efficiency (of immobilized enzyme.
(3) animal-plant oil and the methyl alcohol of coming from the diffusion of film opposite side carry out alcoholysis reaction on the film surface.Because methanol concentration is lower, can eliminate the methyl alcohol that exists in the traditional technology restraining effect to lipase activity, improve immobilized enzyme catalysis efficient.
(4) fixed enzyme membrane reactor integrates enzyme catalysis process and membrane sepn process, and realization response catalysis synchronously separates with product, has simplified production of biodiesel technology, enhances productivity.
(5) reaction conditions involved in the present invention is gentle, energy consumption is low, and fixed enzyme membrane reactor can be reused and serialization production, the utilization ratio that greatly improves enzyme with reduce production costs.
Description of drawings:
Fig. 1 is a production biofuel device synoptic diagram of the present invention.
In the accompanying drawing: 1. be the methyl alcohol storage tank; 2. be the animal-plant oil storage tank; 3. be the film reaction device; 4. be that film reaction device film is inboard; 5. be the film reaction device film outside; 6. be fixed enzyme membrane; 7. be glycerin separator; 8. be biological diesel oil tank.
Embodiment
Following embodiment is done more detailed description to the present invention, but said example is not construed as limiting the invention.
Embodiment 1
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/Rocryl 400 terpolymer of 200,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the N.In spinning voltage is that 7kV, spinning nozzle solution flow are that 0.1mL/h, receiving range are under the 8cm condition; Carrying out electrostatic spinning and process Fibre diameter 1000nm ultra-fine fibre composite package, is propping material with the polyester non-woven fabric, and it is loaded in inside and outside double cylinder-shaped film tool; Form the film reaction device 3.; Shown in accompanying drawing, 4. the inner cylinder of this membrane module is inner claims membrane module film inboard, and 5. cavity claims the membrane module film outside between the inside and outside cylinder side face.3 membrane module polyphones are constituted one, two, three membrane reactor.Adopting the mode of cross flow filter earlier epoxy chloropropane to be circulated in membrane reactor device under 30 ℃ 1 hour, is that the lipase solution of 5g/L circulated in membrane reactor device under 30 ℃ 1 hour with concentration again; 4. epoxy chloropropane and lipase solution all get into the film inboard via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor, form three grades of enzyme mebrane reactors; To inject enzyme membrane device film inboard 4. with the flow velocity of 0.1L/h through animal-plant oil mixing solutions that filter to handle, 5. inject methyl alcohol in the enzyme membrane device film outside simultaneously with the flow velocity of 0.1L/h.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/Rocryl 400 terpolymer of 150,000 is dissolved in and is made into the spinning solution that concentration is 5wt.% in the N.In spinning voltage is that 8kV, spinning nozzle solution flow are that 1mL/h, receiving range are under the 10cm condition; Carry out electrostatic spinning and process Fibre diameter 500nm ultra-fine fibre composite package; With the polyester non-woven fabric is propping material; It is loaded in the rolled film tool, a plurality of film tool polyphones are constituted one, two, three membrane reactor.Adopting the mode of cross flow filter earlier epoxy chloropropane to be circulated in membrane reactor device under 27 ℃ 1.5 hours, is that the lipase solution of 8g/L circulated in membrane reactor device under 27 ℃ 1.5 hours with concentration again; 4. epoxy chloropropane and lipase solution all get into membrane module film inboard via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor, form three grades of enzyme mebrane reactors; To inject enzyme membrane device film inboard 4. with the flow velocity of 1L/h through animal-plant oil mixing solutions that filter to handle, 5. inject methyl alcohol in the enzyme membrane device film outside simultaneously with the flow velocity of 1L/h.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; The effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage and irritates 1. after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/Rocryl 400 terpolymer of 100,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the N.In spinning voltage is that 10kV, spinning nozzle solution flow are that 2mL/h, receiving range are under the 25cm condition; Carry out electrostatic spinning and process Fibre diameter 200nm ultra-fine fibre composite package; With the polyester non-woven fabric is propping material; It is loaded in the rolled film tool, a plurality of film tool polyphones are constituted one, two, three enzyme mebrane reactor.Adopting the mode of cross flow filter earlier epoxy chloropropane to be circulated in membrane reactor device under 25 ℃ 2 hours, is that the lipase solution of 10g/L circulated in membrane reactor device under 25 ℃ 2 hours with concentration again; 4. epoxy chloropropane and lipase solution all get into membrane module film inboard via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor, form three grades of enzyme mebrane reactors; To inject enzyme membrane device film inboard 4. with the flow velocity of 2L/h through animal-plant oil mixing solutions that filter to handle, 5. inject methyl alcohol in the enzyme membrane device film outside simultaneously with the flow velocity of 2L/h.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/Rocryl 400 terpolymer of 50,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the N.In spinning voltage is that 12kV, spinning nozzle solution flow are that 2mL/h, receiving range are under the 25cm condition; Carry out electrostatic spinning and process Fibre diameter 100nm ultra-fine fibre composite package; With the polyester non-woven fabric is propping material; It is loaded in the rolled film tool, a plurality of film tool polyphones are constituted one, two, three enzyme mebrane reactor.Adopting the mode of cross flow filter earlier epoxy chloropropane to be circulated in membrane reactor device under 23 ℃ 2.5 hours, is that the lipase solution of 12g/L circulated in membrane reactor device under 23 ℃ 2.5 hours with concentration again; 4. epoxy chloropropane and lipase solution all get into membrane module film inboard via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor, form three grades of enzyme mebrane reactors; To inject enzyme membrane device film inboard 4. with the flow velocity of 4L/h through animal-plant oil mixing solutions that filter to handle, 5. inject methyl alcohol in the enzyme membrane device film outside simultaneously with the flow velocity of 4L/h.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/Rocryl 400 terpolymer of 50,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the N.In spinning voltage is that 15kV, spinning nozzle solution flow are that 2mL/h, receiving range are under the 25cm condition; Carry out electrostatic spinning and process Fibre diameter 50nm ultra-fine fibre composite package; With the polyester non-woven fabric is propping material; It is loaded in the rolled film tool, a plurality of film tool polyphones are constituted one, two, three enzyme mebrane reactor.Adopting the mode of cross flow filter earlier epoxy chloropropane to be circulated in membrane reactor device under 20 ℃ 3 hours, is that the lipase solution of 15g/L circulated in membrane reactor device under 20 ℃ 3 hours with concentration again; 4. epoxy chloropropane and lipase solution all get into membrane module film inboard via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor, form three grades of enzyme mebrane reactors; To inject enzyme membrane device film inboard 4. with the flow velocity of 5L/h through animal-plant oil mixing solutions that filter to handle, 5. inject methyl alcohol in the enzyme membrane device film outside simultaneously with the flow velocity of 5L/h.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer of 200,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the N.In spinning voltage is that 7kV, spinning nozzle solution flow are that 0.1mL/h, receiving range are under the 8cm condition; Carry out electrostatic spinning and process Fibre diameter 1000nm ultra-fine fibre composite package; With the polyester non-woven fabric is propping material; It is loaded in the rolled film tool, a plurality of film tool polyphones are constituted one, two, three enzyme mebrane reactor.Adopting the mode of cross flow filter earlier LUTARALDEHYDE to be circulated in membrane reactor device under 30 ℃ 1 hour, is that the lipase solution of 5g/L circulated in membrane reactor device under 30 ℃ 1 hour with concentration again; 4. epoxy chloropropane and lipase solution all get into membrane module film inboard via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor, form three grades of enzyme mebrane reactors; To inject enzyme membrane device film inboard 4. with the flow velocity of 0.1L/h through animal-plant oil mixing solutions that filter to handle, 5. inject methyl alcohol in the enzyme membrane device film outside simultaneously with the flow velocity of 0.1L/h.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer of 150,000 is dissolved in and is made into the spinning solution that concentration is 5wt.% in the N.In spinning voltage is that 8kV, spinning nozzle solution flow are that 1mL/h, receiving range are under the 10cm condition; Carry out electrostatic spinning and process Fibre diameter 500nm ultra-fine fibre composite package; With the polyester non-woven fabric is propping material; It is loaded in the rolled film tool, a plurality of film tool polyphones are constituted one, two, three enzyme mebrane reactor.Adopting the mode of cross flow filter earlier LUTARALDEHYDE to be circulated in membrane reactor device under 27 ℃ 1.5 hours, is that the lipase solution of 8g/L circulated in membrane reactor device under 27 ℃ 1.5 hours with concentration again; 4. epoxy chloropropane and lipase solution all get into membrane module film inboard via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor, form three grades of enzyme mebrane reactors; To inject enzyme membrane device film inboard 4. with the flow velocity of 1L/h through animal-plant oil mixing solutions that filter to handle, 5. inject methyl alcohol in the enzyme membrane device film outside simultaneously with the flow velocity of 1L/h.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer of 100,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the N.In spinning voltage is that 10kV, spinning nozzle solution flow are that 2mL/h, receiving range are under the 25cm condition; Carry out electrostatic spinning and process Fibre diameter 200nm ultra-fine fibre composite package; With the polyester non-woven fabric is propping material; It is loaded in the rolled film tool, a plurality of film tool polyphones are constituted one, two, three enzyme mebrane reactor.Adopting the mode of cross flow filter earlier LUTARALDEHYDE to be circulated in membrane reactor device under 25 ℃ 2 hours, is that the lipase solution of 80g/L circulated in membrane reactor device under 25 ℃ 2 hours with concentration again; 4. epoxy chloropropane and lipase solution all get into membrane module film inboard via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor, form three grades of enzyme mebrane reactors; To inject enzyme membrane device film inboard 4. with the flow velocity of 2L/h through animal-plant oil mixing solutions that filter to handle, 5. inject methyl alcohol in the enzyme membrane device film outside simultaneously with the flow velocity of 2L/h.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates.
Embodiment 9
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer of 50,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the N.In spinning voltage is that 12kV, spinning nozzle solution flow are that 2mL/h, receiving range are under the 25cm condition; Carry out electrostatic spinning and process Fibre diameter 100nm ultra-fine fibre composite package; With the polyester non-woven fabric is propping material; It is loaded in the rolled film tool, a plurality of film tool polyphones are constituted one, two, three enzyme mebrane reactor.Adopting the mode of cross flow filter earlier LUTARALDEHYDE to be circulated in membrane reactor device under 23 ℃ 2.5 hours, is that the lipase solution of 12g/L circulated in membrane reactor device under 23 ℃ 2.5 hours with concentration again; 4. epoxy chloropropane and lipase solution all get into membrane module film inboard via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor, form three grades of enzyme mebrane reactors; To inject enzyme membrane device film inboard 4. with the flow velocity of 4L/h through animal-plant oil mixing solutions that filter to handle, 5. inject methyl alcohol in the enzyme membrane device film outside simultaneously with the flow velocity of 4L/h.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates.
Embodiment 10
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer of 50,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the N.In spinning voltage is that 15kV, spinning nozzle solution flow are that 2mL/h, receiving range are under the 25cm condition; Carry out electrostatic spinning and process Fibre diameter 50nm ultra-fine fibre composite package; With the polyester non-woven fabric is propping material; It is loaded in the rolled film tool, a plurality of film tool polyphones are constituted one, two, three enzyme mebrane reactor.Adopting the mode of cross flow filter earlier LUTARALDEHYDE to be circulated in membrane reactor device under 20 ℃ 3 hours, is that the lipase solution of 15g/L circulated in membrane reactor device under 20 ℃ 3 hours with concentration again; 4. epoxy chloropropane and lipase solution all get into membrane module film inboard via the ultra-fine fibre fenestra in the working cycle, thereby realize the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor, form three grades of enzyme mebrane reactors; To inject enzyme membrane device film inboard 4. with the flow velocity of 5L/h through animal-plant oil mixing solutions that filter to handle, 5. inject methyl alcohol in the enzyme membrane device film outside simultaneously with the flow velocity of 5L/h.4. methyl alcohol constantly penetrate into enzyme membrane device film inboard, through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside 5..It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and 1. the effusive reaction solution in the first step reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and 1. the effusive reaction solution in the second stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be our title product---biofuel, get into the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage tank after glycerine separates.
The biofuel results of property that table 1 embodiment is produced
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| Density (25 ℃, g/cm 3) | 0.8674 | 0.8712 | 0.8733 | 0.8619 | 0.8832 | 0.8778 | 0.8802 | 0.8592 | 0.8612 | 0.8699 |
| Viscosity (25 ℃, mm 2/s) | 4.821 | 4.832 | 4.846 | 4.809 | 4.855 | 4.840 | 4.853 | 4.798 | 4.801 | 4.860 |
| Lightning (℃) | ＞150 | ＞150 | ＞150 | ＞150 | ＞150 | ＞150 | ＞150 | ＞150 | ＞150 | ＞150 |
| S content (ppm) | ＜3 | ＜3 | ＜3 | ＜3 | ＜3 | ＜3 | ＜3 | ＜3 | ＜3 | ＜3 |
| Carboloy residue (mass%) | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 |
| Cetane value | 74.3 | 74.2 | 74.4 | 74.4 | 74.2 | 74.2 | 74.4 | 74.5 | 74.3 | 74.4 |
| Water-content (ppm) | ＜300 | ＜300 | ＜300 | ＜300 | ＜300 | ＜300 | ＜300 | ＜300 | ＜300 | ＜300 |
| Total acid value (mg KOH/g) | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 |
| Methanol content (mass%) | ＜0.06 | ＜0.06 | ＜0.06 | ＜0.06 | ＜0.06 | ＜0.06 | ＜0.06 | ＜0.06 | ＜0.06 | ＜0.06 |
| Methyl esters content (mass%) | ＞99.5 | ＞99.5 | ＞99.5 | ＞99.5 | ＞99.5 | ＞99.5 | ＞99.5 | ＞99.5 | ＞99.5 | ＞99.5 |
| Content of monoglyceride (mass%) | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 |
| Diacylglycerol content (mass%) | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 |
| Triglyceride content (mass%) | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 |
| Free glycerol content (mass%) | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 | ＜0.01 |
| Total glycerol content (mass%) | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 | ＜0.05 |
| P content (ppm) | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Heat (kJ/g) | 35.87 | 35.91 | 35.94 | 35.80 | 35.98 | 35.95 | 35.97 | 35.72 | 35.79 | 35.89 |
Claims (10)
1. fixed enzyme membrane reactor; It is characterized in that using the ultra-fine fibre composite package of Fibre diameter as 30-1000nm; With the polyester non-woven fabric is propping material; Double cylinder-shaped film reaction device (3) inside and outside the formation wherein has the film reaction device film inboard (4) and the film reaction device film outside (5), and inboard (4) fiber surface of film is activated and lipase immobilization; 3 film reaction devices (3) are concatenated into one, two, three enzyme mebrane reactor.
2. prepare the method for the said fixed enzyme membrane reactor of claim 1, may further comprise the steps:
(1) preparation of membrane reactor: vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/Rocryl 400 or vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer be dissolved in process spinning solution in the solvent and carry out electrostatic spinning and become the ultra-fine fibre composite package; With the polyester non-woven fabric is propping material, it is loaded in inside and outside double cylinder-shaped film tool, form the film reaction device;
(2) preparation of enzyme mebrane reactor: the mode that adopts cross flow filter is successively with epoxy chloropropane or LUTARALDEHYDE and lipase solution injection membrane reactor; In membrane reactor, circulate; Solution gets into film inner layer (4) via the ultra-fine fibre fenestra in the working cycle, thereby realizes the activation and the enzyme immobilization on ultra-fine fibre surface in the membrane reactor.
3. by the described preparation method of claim 2; It is characterized in that: in the described vinyl cyanide of step (1)/2-methacryloxypropyl-ethyl-phosphatidylcholine/Rocryl 400 or vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer; 2-methacryloxypropyl-ethyl-phosphatidylcholine mole percent level is 1～15%; The mole percent level of Rocryl 400 or aminoethyl methacrylate is 1～15%, and its viscosity-average molecular weight is 5～200,000.
4. by the described preparation method of claim 2, it is characterized in that: the described solvent of step (1) is a kind of or more multiple than blended with arbitrarily in DMSO 99.8MIN., N or the N,N-DIMETHYLACETAMIDE.
5. by the described preparation method of claim 2, it is characterized in that: the described electrostatic spinning voltage of step (1) is that 5kV～20kV, spinning nozzle solution flow are that 0.1mL/h～2.0mL/h, receiving range are 5cm～25cm, makes superfine fibre film.
6. by the described preparation method of claim 2; It is characterized in that: step (2) is described carries out working cycle and is in membrane reactor: earlier epoxy chloropropane or LUTARALDEHYDE were circulated in membrane reactor device under 20～30 ℃ 1～3 hour, lipase solution was circulated in membrane reactor device under 20～30 ℃ 1～3 hour again.
7. by the described preparation method of claim 2, it is characterized in that: lipase solution is that lypase is dissolved in the pH value is to process in 7.0 the phosphate buffer soln.
8. the application of described fixed enzyme membrane reactor of claim 1 or the fixed enzyme membrane reactor processed by the fixed enzyme membrane reactor preparation method of claim 2; With its production biofuel; Comprising the steps: will be through filtering the animal-plant oil mixing solutions of handling; Inject enzyme membrane device tunica fibrosa inboard (4), inject methyl alcohol in the enzyme membrane device tunica fibrosa outside (5) simultaneously; Methyl alcohol constantly penetrates into enzyme membrane device film inboard (4), through fixed lipase catalyzed, the alcoholysis reaction of animal-plant oil takes place on the internal membrane surface, and the glycerine that reaction generates sees through film and gets into the enzyme membrane device film outside (5); It is inboard directly to get into second stage reactor drum film from the inboard effusive reaction solution of first step reactor drum film, and the effusive reaction solution in the first step reactor drum film outside gets into methyl alcohol storage tank (1) after glycerine separates; The inboard effusive reaction solution of reactor drum film directly gets into third stage reactor drum film inboard from the second stage, and the effusive reaction solution in the second stage reactor drum film outside gets into methyl alcohol storage tank (1) after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor drum film, be title product--biofuel gets into the biofuel storage and irritates (8); The effusive reaction solution in the third stage reactor drum film outside gets into the methyl alcohol storage and irritates (1) after glycerine separates.
9. the application of fixed enzyme membrane reactor according to claim 8 is characterized in that: it is that 70～80% animal-plant oil and mass ratio are the mixing solutions that 20～30% ordinary diesel oil is formed that the animal-plant oil mixing solutions is meant by mass ratio.
10. it is characterized in that according to Claim 8 or the application of 9 described fixed enzyme membrane reactors: the flow velocity that injects the inboard animal-plant oil mixing solutions of membrane module tunica fibrosa is 0.1～5L/h; The flow velocity that injects membrane module tunica fibrosa outside methyl alcohol is 0.1～5L/h.
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| CN101538590B (en) * | 2009-04-30 | 2012-04-04 | 浙江大学 | Technology for catalyzing oil hydrolysis by using immobilized lipase |
| CN101693873B (en) * | 2009-10-15 | 2011-12-28 | 天津大学 | Sandwich structuralized enzymatic membrane reactor, production method and application thereof |
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| CN103553921B (en) * | 2013-11-20 | 2015-10-28 | 山东理工大学 | Continuously dehydrating esterification device is utilized to carry out the method for continuous esterification |
| CN104646060A (en) * | 2014-12-01 | 2015-05-27 | 天津工业大学 | Alkaline catalytic membrane |
| CN105040278B (en) * | 2015-07-24 | 2017-08-25 | 河南工程学院 | For the preparation method for the composite nano-fiber membrane for producing biodiesel |
| CN105038996B (en) * | 2015-07-24 | 2019-01-11 | 河南工程学院 | Nano-fiber composite film reactor |
| RU2665041C2 (en) * | 2016-12-30 | 2018-08-27 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Method for obtaining biodiesel fuel |
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