CN101235351A - 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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- CN101235351A CN101235351A CNA2008100597765A CN200810059776A CN101235351A CN 101235351 A CN101235351 A CN 101235351A CN A2008100597765 A CNA2008100597765 A CN A2008100597765A CN 200810059776 A CN200810059776 A CN 200810059776A CN 101235351 A CN101235351 A CN 101235351A
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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 obtaining from reproducible biomass resource is similar to petroleum diesel, and its main component 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 engine; 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 complexity, 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, is subject to people's attention day by day.CN1436834 is acyl acceptor with the short-chain aliphatic ester, utilize renewable resources production biofuel such as biological enzyme animal-plant oil under suitable temperature range.CN1640991 will add methyl alcohol or ethanol through the raw material animal-plant oil of filtration and emulsification, utilize immobilized lipase catalyzed transesterification on the organic solvent oil-water interface in encloses container.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 reclaim repeated use from reaction system 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 be 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 the superfine fibrous membrane materials of high-specific surface area, high voidage and fabulous hole connectedness, 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
Purpose of the present invention will be a mould material with ultra-fine fibre 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.
The technical scheme of taking for achieving the above object:
One, the constructional feature of fixed enzyme membrane reactor of the present invention is to be the ultra-fine fibre composite membrane of 30-1000nm with Fibre diameter, with the polyester non-woven fabric is propping material, constitute inside and outside double cylinder-shaped film reaction device, 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 processing step:
(1) vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/hydroxyethyl methylacrylate 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 make the ultra-fine fibre composite membrane, 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/hydroxyethyl methylacrylate 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 hydroxyethyl methylacrylate (or aminoethyl methacrylate) mole percent level is 1～15%.
Described solvent is a kind of in dimethyl sulfoxide (DMSO), dimethyl formamide or the N,N-DIMETHYLACETAMIDE or with more multiple than blended arbitrarily;
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 membrane 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 glutaraldehyde 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 glutaraldehyde and lipase solution all enter 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 lipase is dissolved in the pH value is to make 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: the animal-plant oil mixing solutions that will handle after filtration, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor film outside enters 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 by the immobilization of chemical covalent method reality enzyme, and zymoprotein and carrier are not easy desorption by covalent bonds.
(2) used electrostatic spinning ultra-fine fibre composite membrane 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 gentleness, energy consumption involved in the present invention are low, and fixed enzyme membrane reactor can be reused and serialization production, greatly improve enzyme utilization ratio and 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 film reaction device film 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 described example is not construed as limiting the invention.
Embodiment 1
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/hydroxyethyl methylacrylate terpolymer of 200,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the dimethyl formamide.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 make Fibre diameter 1000nm ultra-fine fibre composite membrane, 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 3., as shown in drawings, 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 again with concentration; 4. epoxy chloropropane and lipase solution all enter 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; 4. the animal-plant oil mixing solutions handled is after filtration injected enzyme membrane device film inboard with the flow velocity of 0.1L/h, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor film outside enters the methyl alcohol storage tank after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/hydroxyethyl methylacrylate terpolymer of 150,000 is dissolved in and is made into the spinning solution that concentration is 5wt.% in the dimethyl formamide.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 make Fibre diameter 500nm ultra-fine fibre composite membrane, 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 again with concentration; 4. epoxy chloropropane and lipase solution all enter 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; 4. the animal-plant oil mixing solutions handled is after filtration injected enzyme membrane device film inboard with the flow velocity of 1L/h, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; The effusive reaction solution in the third stage reactor film outside enters the methyl alcohol storage and irritates 1. after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/hydroxyethyl methylacrylate terpolymer of 100,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the dimethyl formamide.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 make Fibre diameter 200nm ultra-fine fibre composite membrane, 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 again with concentration; 4. epoxy chloropropane and lipase solution all enter 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; 4. the animal-plant oil mixing solutions handled is after filtration injected enzyme membrane device film inboard with the flow velocity of 2L/h, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor film outside enters the methyl alcohol storage tank after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/hydroxyethyl methylacrylate terpolymer of 50,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the dimethyl formamide.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 make Fibre diameter 100nm ultra-fine fibre composite membrane, 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 again with concentration; 4. epoxy chloropropane and lipase solution all enter 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; 4. the animal-plant oil mixing solutions handled is after filtration injected enzyme membrane device film inboard with the flow velocity of 4L/h, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor film outside enters the methyl alcohol storage tank after glycerine separates.
With molecular weight is that vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/hydroxyethyl methylacrylate terpolymer of 50,000 is dissolved in and is made into the spinning solution that concentration is 4wt.% in the dimethyl formamide.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 make Fibre diameter 50nm ultra-fine fibre composite membrane, 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 again with concentration; 4. epoxy chloropropane and lipase solution all enter 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; 4. the animal-plant oil mixing solutions handled is after filtration injected enzyme membrane device film inboard with the flow velocity of 5L/h, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor film outside enters 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 dimethyl formamide.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 make Fibre diameter 1000nm ultra-fine fibre composite membrane, 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 glutaraldehyde 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 again with concentration; 4. epoxy chloropropane and lipase solution all enter 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; 4. the animal-plant oil mixing solutions handled is after filtration injected enzyme membrane device film inboard with the flow velocity of 0.1L/h, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor film outside enters 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 dimethyl formamide.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 make Fibre diameter 500nm ultra-fine fibre composite membrane, 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 glutaraldehyde 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 again with concentration; 4. epoxy chloropropane and lipase solution all enter 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; 4. the animal-plant oil mixing solutions handled is after filtration injected enzyme membrane device film inboard with the flow velocity of 1L/h, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor film outside enters 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 dimethyl formamide.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 make Fibre diameter 200nm ultra-fine fibre composite membrane, 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 glutaraldehyde 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 again with concentration; 4. epoxy chloropropane and lipase solution all enter 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; 4. the animal-plant oil mixing solutions handled is after filtration injected enzyme membrane device film inboard with the flow velocity of 2L/h, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor film outside enters 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 dimethyl formamide.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 make Fibre diameter 100nm ultra-fine fibre composite membrane, 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 glutaraldehyde 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 again with concentration; 4. epoxy chloropropane and lipase solution all enter 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; 4. the animal-plant oil mixing solutions handled is after filtration injected enzyme membrane device film inboard with the flow velocity of 4L/h, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor film outside enters 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 dimethyl formamide.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 make Fibre diameter 50nm ultra-fine fibre composite membrane, 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 glutaraldehyde 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 again with concentration; 4. epoxy chloropropane and lipase solution all enter 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; 4. the animal-plant oil mixing solutions handled is after filtration injected enzyme membrane device film inboard with the flow velocity of 5L/h, 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 enters the enzyme membrane device film outside 5..Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, 1. the effusive reaction solution in the first step reactor film outside enters the methyl alcohol storage tank after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, 1. the effusive reaction solution in the second stage reactor film outside enters the methyl alcohol storage tank after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be our target product---biofuel, enter the biofuel basin 8.; 1. the effusive reaction solution in the third stage reactor film outside enters 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, a kind of fixed enzyme membrane reactor, it is characterized in that with Fibre diameter being the ultra-fine fibre composite membrane of 30-1000nm, with the polyester non-woven fabric is propping material, constitute inside and outside double cylinder-shaped film reaction device (3), film reaction device film inboard (4) and the film reaction device film outside (5) is wherein arranged, and film inboard (4) fiber surface is activated and enzyme immobilization; 3 film reaction devices (3) are concatenated into one, two, three enzyme mebrane reactor.
2, the preparation method of the fixed enzyme membrane reactor of claim 1 may further comprise the steps:
(1) preparation of membrane reactor: vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/hydroxyethyl methylacrylate or vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer be dissolved in make spinning solution in the solvent and carry out electrostatic spinning and become the ultra-fine fibre composite membrane, with the polyester non-woven fabric is propping material, it is loaded form the film reaction device in inside and outside double cylinder-shaped film tool;
(2) preparation of enzyme mebrane reactor: the mode that adopts cross flow filter is successively with epoxy chloropropane or glutaraldehyde and lipase solution injection membrane reactor, in membrane reactor, circulate, solution enters 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: the described vinyl cyanide of step (1)/2-methacryloxypropyl-ethyl-phosphatidylcholine/hydroxyethyl methylacrylate or vinyl cyanide/2-methacryloxypropyl-ethyl-phosphatidylcholine/aminoethyl methacrylate terpolymer: 2-methacryloxypropyl-ethyl in the multipolymer-phosphatidylcholine mole percent level is 1～15%, the mole percent level of hydroxyethyl methylacrylate 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 in dimethyl sulfoxide (DMSO), dimethyl formamide or the N,N-DIMETHYLACETAMIDE or with more multiple than blended arbitrarily.
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 glutaraldehyde 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 lipase is dissolved in the pH value is to make 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 made by the fixed enzyme membrane reactor preparation method of claim 2, with its production biofuel, comprise the steps: the animal-plant oil mixing solutions that to handle after filtration, 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 enters the enzyme membrane device film outside (5).Directly enter reactor film inboard, the second stage from the inboard effusive reaction solution of first step reactor film, the effusive reaction solution in the first step reactor film outside enters methyl alcohol storage tank (1) after glycerine separates; Directly enter third stage reactor film inboard from the inboard effusive reaction solution of second stage reactor film, the effusive reaction solution in the second stage reactor film outside enters methyl alcohol storage tank (1) after glycerine separates; Collect the inboard effusive reaction solution of third stage reactor film, be target product---biofuel enters the biofuel storage and irritates (8); The effusive reaction solution in the third stage reactor film outside enters 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, according to Claim 8 or the application of 9 described fixed enzyme membrane reactors, it is characterized in that: 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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