CN1648207A - Process for coupling producing bioloigical diesel oil and 1,3-propylene glycol - Google Patents

Process for coupling producing bioloigical diesel oil and 1,3-propylene glycol Download PDF

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CN1648207A
CN1648207A CNA2004101004792A CN200410100479A CN1648207A CN 1648207 A CN1648207 A CN 1648207A CN A2004101004792 A CNA2004101004792 A CN A2004101004792A CN 200410100479 A CN200410100479 A CN 200410100479A CN 1648207 A CN1648207 A CN 1648207A
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ammediol
membrane
film
oil
lipase
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CN1276962C (en
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修志龙
牟英
张代佳
孙亚琴
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Dalian University of Technology
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    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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Abstract

The present invention belongs to the field of bioengineering technology, and especially a kind of couple producing biological diesel oil and 1, 3-propylene glycol. The present invention features that the course of lipase catalyzed reaction between methanol or ethanol and fat to produce biological diesel oil and the course of biologically converting glycerin into 1, 3-propylene glycol are coupled via membrane filtering for simultaneous proceeding. The present invention has the effects of eliminating the suppression of short-chain alcohol and glycerin on lipase, prolonging the service life of immobilized enzyme, omitting the glycerin separating and extracting step, lowering the production cost, saving time, raising production efficiency and providing economic and feasible process for producing biological diesel oil and 1, 3-propylene glycol.

Description

A kind of coupling production biofuel and 1, the method for ammediol
Technical field
The invention belongs to technical field of bioengineering, specially refer to a kind of coupling method production biofuel and 1, the method for ammediol.
Background technology
Biofuel is meant by reproducible glyceride stock by the long chain fatty acid ester that transesterification reaction obtains, and is a kind ofly can substitute the environment friendly fuel that ordinary diesel oil is used.At present, the prospective oil in the world reduces gradually, and the environmental pollution that oil product burning back exhaust gas discharged causes also is the big problem that the mankind face, and therefore, developing the substituting fuel of environmental-protective and regenerative has become one of current most important problem.
At present, production method of bio-diesel oil mainly contains chemical method and biological enzyme.Chemical method adopts excessive methyl alcohol or ethanol to react with grease under sodium hydroxide or potassium hydroxide catalysed, High Temperature High Pressure can fast reaction speed, alcohol excessive help the reaction carry out to positive dirction, but need after reaction finishes to wash with water, acid neutralization, distillation reclaim excessive pure and mild by-product glycerin, contain salt in the raw glycerine that obtains, be difficult to direct utilization, the purification of glycerin power consumption is bigger, cause the refining glycerine price higher, and discharging of waste liquid is arranged.Biological enzyme is to utilize lipase that the glycerine in methyl alcohol or ethanol and the grease is exchanged to form fatty acid methyl ester or ethyl ester (biofuel) and by-product glycerin, this method has advantages such as reaction conditions gentleness, pure consumption are few, non-pollutant discharge, but the reaction times is longer, the enzyme price is higher, and methyl alcohol and ethanol have restraining effect to the activity of lipase.Usually adopt the method for immobilized enzyme to solve the problem that enzyme uses repeatedly, but by-product glycerin has influenced mass transfer and enzyme catalysis efficient easily attached to carrier surface, brings difficulty to scale operation.
By-product glycerin in the production of biodiesel process is a fermentative Production 1, the raw material of ammediol, and 1, ammediol is a kind of important chemical material, can be used as organic solvent and be applied to industries such as printing ink, printing and dyeing, coating, lubricant, antifreezing agent, go back the useful as drug synthetic intermediate.1, the topmost purposes of ammediol is the macromolecular material as the synthetic excellent performance of polymer monomer, not only can make polyester plastics have the biodegradable characteristic of natural circulation, and be the important monomer raw material of the new type polyester fiber polytrimethylene terephthalate (PTT) of manufacturing property excellence, alternative ethylene glycol, 1, the 2-propylene glycol, 1, intermediates such as 4-butyleneglycol are produced polyester and are extended agent as carbochain.PTT is a kind of new polyester man-made fiber in the textile industry, have many good performances, the good continuous printing and dyeing that present as need not to add any speciality chemical in the tint permanence of recovery of elasticity, uvioresistant, ozone and the oxynitride of nylon sample, low static, low water absorption, the panchromatic scope etc.It has broad application prospects, and is the focus of present synthon new varieties, therefore, 1 of developing low-cost, ammediol has become the hot issue that researcher is paid close attention to.With glycerine is that raw material generates 1 by microbial transformation, and the research of ammediol starts from 1881, but just causes people's attention gradually up to the eighties in 20th century.Compare with the chemical synthesis that with the oil is raw material, biological process has the renewable resources of utilization, reaction conditions gentleness, easy to operate and safe, characteristics such as by product is few, non-environmental-pollution, but the higher price of its raw material glycerine becomes microbial method produces 1, the obstacle of ammediol industrialization maximum, and the by-product glycerin saliferous of chemical method production biofuel is more, be unfavorable for directly utilizing it to produce 1 ammediol.
In order to address the above problem, the present invention adopts biological enzyme catalyst grease and methyl alcohol or ethanol synthesis to generate biofuel, utilize hydrophilic ultrafiltration membrane that by-product glycerin is separated simultaneously, through microbial transformation is 1, ammediol, two processes of enzyme catalysis and microbial transformation are carried out simultaneously, realize biofuel and 1, the coupling production of ammediol.
Summary of the invention
The object of the present invention is to provide a kind of coupling production biofuel and 1, the technology of ammediol, the reaction of lipase-catalyzed short chain alcohol and grease is generated biofuel and microbial transformation glycerine is 1, two processes of ammediol are got up by the ultra-filtration membrane coupling, and two processes are carried out simultaneously.In the production of biodiesel process, short chain alcohol adopts the mode of segmentation or dropping continuously to add, and can avoid excessive organic solvent to cause poisoning by enzyme like this; Can in time remove by-product glycerin in the production of biodiesel process by the ultra-filtration membrane diafiltration, prolong the work-ing life of immobilized enzyme; Glycerine directly is converted into 1 through microorganism cells, ammediol, and the separation and purification operation of having exempted glycerine has reduced and has produced 1, and the raw materials cost of ammediol has been saved the time, has improved production efficiency.
Technical scheme of the present invention is at first to adopt catalyzed by biological enzyme that the grease transesterification is generated biofuel, utilize hydrophilic hollow fiber ultrafiltration membrane or flat sheet membrane that by-product glycerin is separated simultaneously, opposite side at film is 1 with transformation of glycerol directly with microorganism, ammediol.
The step that realizes the inventive method is as follows:
1) preparation of microbiological culture media: must possess the required nutritive ingredient of microorganism growth in the substratum, as carbon sources such as glucose or glycerine, nitrogenous source and phosphoric acid salt (phosphorus source) and vitriol (sulphur source) etc. such as urea, ammonium salt, yeast extract or yeast powder.Also need positively charged ion and trace elements such as zinc, iron, manganese, copper, cobalt, boron and molybdenum such as sodium, potassium, magnesium, calcium in addition, every kind of content of elements greatly in the scope of 0.01mg/L～50mg/L, substratum need 120 ℃ down sterilization can use in 15～20 minutes.
2) seed culture: carry out in shaking bottle, shaking speed is 100～300r/min, and temperature is 27～40 ℃, and incubation time is 9～30h.Microorganism cells is Cray Bai Shi bacillus (Klebsiella pneumoniae), lemon bacterium (Citrobacter) or clostridium butyricum (Clostridium butyricum).
3) fermentation culture: carry out in cell culture apparatus, inoculum size is 5%～20%, and mixing speed is 100～400r/min, and temperature is 27～40 ℃.Can lead to nitrogen or air in the fermenting process in incubator, air flow is 0.2～4vvm.Fermentation mode adds fermentation for batch formula stream, and the time of fermentation is 10～70h.1, ammediol ferment glycerin starting point concentration is 2～15%, and pH is 6～8, product 1, and the concentration of ammediol can reach 10～85g/L.
4) enzyme catalysis and microbial transformation coupling process: will add in the enzyme reactor through the immobilized enzyme that pre-treatment is removed the raw oil material of impurity and accounted for oil quality 10～30%, control reaction temperature is 30～60 ℃, add methyl alcohol or ethanol when stirring, mixing speed is 100～300r/min, methyl alcohol or ethanol adopt the mode of segmentation or dropping continuously to add, segmentation adds and can be divided into 3～30 sections, drips methyl alcohol continuously and the alcoholic acid dilution rate is respectively 0.003～0.02h -1With 0.005～0.03h -1After 1～5h is carried out in reaction, reaction solution is pumped into (not containing immobilized enzyme) side of wetting ability flat plate ultrafiltration membrane or hollow-fibre membrane with recycle pump, the opposite side of film is above-mentioned 1, the fermented liquid of ammediol (containing microorganism cells), entire reaction course 15～50h, greasy transformation efficiency can reach 80～97%, and the utilization ratio of glycerine reaches 90～99%.
Used lipase derives from the immobilized lipase of meter black wool mould (Mucor miehei), fold candida (Candidaantarctica), cylindrulite candiyeast (Candida Cylindracea), raw oil material is waste oil, rapeseed oil, soybean oil, Oleum Verniciae fordii, plam oil, coptis wood oil, Viscotrol C, engineering microalgae oil, and short chain alcohol is methyl alcohol and ethanol.
5) membrane filtration condition: used ultra-filtration membrane is asymmetric, hydrophilic ultra-filtration membrane, and molecular weight cut off can be flat sheet membrane or hollow-fibre membrane between 10～50kDa.The film both sides pump into enzymic catalytic reaction liquid and 1 respectively, and the ammediol fermented liquid is when using hollow-fibre membrane, the suggestion tube side is walked enzymic catalytic reaction liquid, shell side walks 1, the ammediol fermented liquid, and film both sides liquid flow rate is respectively 3.6～7.2h with the ratio of the volume of enzyme reactor or cell culture apparatus -1With 4.8～9.6h -1The working pressure of film is 0.1MPa～0.5Mpa, and the pressure of both sides is approaching, and the pressure of reaction solution one side is a little more than fermented liquid (0.001MPa～0.05Mpa).The service temperature of film depends on the temperature of cell cultures, is generally 27～40 ℃, and the temperature of reaction solution one side is a little more than fermented liquid, and the temperature head of both sides is between 0～5 ℃.When the temperature of both sides differs big, with cooling of the interchanger before and after the film or reacting by heating liquid.
Used mould material is organic membrane or inorganic ceramic film, organic membrane refers to polyethersulfone, cellulose ester, polyimide/polyetherimide, polyester fat acid amides and polyacrylonitrile, and inorganic ceramic film is meant pellumina, titanium dioxide film, silicon dioxide film, zirconium dioxide film and composite membrane thereof.
Effect of the present invention and benefit are to have utilized ultra-filtration membrane with lipase-catalyzed and two process couplings of microbial transformation, realize biofuel and 1, the coproduction of ammediol.In the enzyme catalysis process, adopt the mode of segmentation or dropping continuously to add methyl alcohol or ethanol, can reduce even eliminate the lipase poisoning and deactivation that excessive short chain alcohol causes; Can in time remove the by-product glycerin that forms in the enzyme catalysis process by membrane ultrafiltration, prolong the work-ing life of immobilized enzyme; Glycerine is converted into 1 at the opposite side of film through microorganism cells, and ammediol has been saved the isolating expense of glycerine, has reduced production cost, shortened the time of whole production, but save energy has improved production efficiency.
Description of drawings
Accompanying drawing is coupling method production biofuel of the present invention and 1, the process flow diagram of ammediol.
Embodiment
Below in detail combination technology scheme and accompanying drawing are described in detail embodiments of the invention.
Embodiment 1:
1) bacterial classification and enzyme: the bacterial classification of fermentation is klebsiella (Klebsiella pneumoniae), is a kind of facultative anaerobe, and available from Chinese common micro-organisms DSMZ (CGMCC), culture presevation number is 1.1736.Immobilized lipase Novozym 435 derives from Candidaantarctica available from Novo Nordisk Co.,Ltd, is fixed on a kind of macroporous acrylic resin.
2) substratum: divide two kinds of seed culture medium and fermention mediums, division is as follows:
A. seed culture medium (1L):
Glycerine: 20g K 2HPO 43H 2O:4.454g
KH 2PO 4：1.3g (NH4) 2SO 4：2.0g
MgSO 47H 2O:0.2g yeast powder: 1.0g
CaCO 3: 2.0g trace element TE1:2mL
2%CaCl 2Solution: 1mL 0.5%FeSO 4Solution: 1mL
Trace element TE1 forms (1L):
Saturated hydrochloric acid: 0.9mL ZnCl 2: 70mg
MnCl 2·4H 2O：100mg H 3BO 3：60mg
CoCl 2·6H 2O：200mg NiCl 2·6H 2O：25mg
NaMoO 4·2H 2O：35mg CuCl 2·2H 2O：20mg
B. fermention medium is formed (1L):
(NH 4) 2SO 4：6.61g KH 2PO 4：1.36g
MgCl 2·6H 2O：0.26g CaCl 2：0.29g
Citric acid: 0.42g yeast powder: 1.0g
Glycerine: 40g trace element TE2:5mL
Trace element TE2 forms (1L):
Saturated hydrochloric acid: 10mL ZnCl 2: 0.379g
FeCl 3·6H 2O：5.4g MnCl 2·4H 2O：0.17g
CoCl 2·6H 2O：0.47g H 3BO 3：0.06g
CuCl 2·2H 2O：0.47g NaMoO 4·2H 2O：0.005g
3) fermenting process: divide two kinds of seed culture and fermentation culture, wherein seed culture is carried out in the triangular flask of 500mL, and liquid amount is 100mL, and shaking speed is 200r/min; Fermentation culture is carried out in the full-automatic cell incubator, and working volume is 2L, and actual liquid amount is 1L, the glycerine starting point concentration is 4%, and inoculum size is 10%, and rotating speed is controlled to be 200r/min, the air flow 0.4vvm of nitrogen, regulating pH with 2mol/L sodium hydroxide is 7.0, temperature is controlled at 37 ℃.
4) the 2kg soybean oil is added in the reactor, the immobilized lipase Novozym435 that adds 300g simultaneously, be heated to 40 ℃, add methyl alcohol 22.3g (molar ratio of methanol to oil is 0.3: 1) and begin reaction, mixing speed is 170r/min in the reaction process, added methyl alcohol once in per 1 hour, add methyl alcohol 266g altogether, force the reaction solution circulation, pass through flat sheet membrane with pump, the opposite side of film is 1, the ammediol fermented liquid.
5) flat sheet membrane is the hydrophilic cellulose acetate membrane of asymmetry, and molecular weight cut off is 40kDa, and area is 400cm 2, operational condition is: 38 ℃ of temperature, and pressure 0.12MPa, esterification liquid and 1, the volume ratio of ammediol fermented liquid flow velocity and reactor is respectively 5.4h -1And 7.2h -1Enzymatic reaction solution is cooled to 38 ± 1 ℃ with interchanger before the film, is heated to 40 ± 2 ℃ with interchanger behind the film excessively.
It is as follows to test resulting result:
30h has been carried out in reaction, and in the fermented liquid 1, the concentration of ammediol is 52.76g/L, and alcohol concn is 7.22g/L, and acetic acid concentration is 4.85g/L, and 2,3-butyleneglycol concentration is 4.28g/L, produces biofuel 1753g.
Embodiment 2:
1) 1, ammediol fermented bacterium, substratum and fermenting process are with embodiment 1.
2) the 2kg rapeseed oil adds in the reactor, adds 320g immobilized lipase Novozym 435 simultaneously, is heated to 45 ℃, add ethanol 11g (molar ratio of methanol to oil is 0.1: 1) and begin reaction, mixing speed is 170r/min in the reaction process, and ethanol adopts the mode that drips to add, and dilution rate is 0.01h -1, add ethanol 380g altogether, force the reaction solution circulation with pump, by hollow-fibre membrane, the opposite side of film is 1, the ammediol fermented liquid.
3) hollow-fibre membrane is a cellulose-acetafolic, and molecular weight cut off is 10kDa, and surface-area is 0.5m 2, working pressure is 0.13Mpa, and temperature is 38 ℃, and the tube side of film is an esterification liquid, and the volume ratio of flow velocity and enzymic catalytic reaction device is 6.0h -1, shell side is 1, the ammediol fermented liquid, and the volume ratio of flow velocity and cell culture apparatus is 8.4h -1
4) enzymatic reaction solution is cooled to 38 ± 1 ℃ with interchanger before the film, is heated to 45 ± 2 ℃ with interchanger behind the film excessively.
The result is as follows for the experiment gained:
34h has been carried out in reaction, and in the fermented liquid 1, the concentration of ammediol is 55.48g/L, and alcohol concn is 10.48g/L, and acetic acid concentration is 6.10g/L, and 2,3-butyleneglycol concentration is 5.10g/L, produces biofuel 1711g.

Claims (1)

1. a coupling production biofuel and 1, the method for ammediol is with lipase-catalyzed short chain alcohol and the grease reaction generates biofuel and microbial transformation glycerine is 1, two processes of ammediol are got up by the membrane filtration coupling, and two processes are carried out simultaneously; The used lipase of enzyme process derives from meter black wool mould (Mucor miehei), fold candida (Candida antarctica), the immobilized lipase of cylindrulite candiyeast (Candida Cylindracea), raw oil material is a waste oil, rapeseed oil, soybean oil, Oleum Verniciae fordii, plam oil, coptis wood oil, Viscotrol C, engineering microalgae oil, short chain alcohol is methyl alcohol and ethanol, the transesterification reaction condition is: 30～60 ℃ of temperature, stirring velocity 100～300r/min, the mode that methyl alcohol or ethanol adopt segmentation or Continuous Flow to add, segmentation stream adds can be divided into 3～30 periods, and dripping the methyl alcohol dilution rate continuously is 0.003～0.02h -1, alcohol dilution speed is 0.005～0.03h -1, the reaction times is 10～30h, transformation efficiency can reach 80～97%; Microbial method is 1 with transformation of glycerol, ammediol, described microorganism is Cray Bai Shi bacillus (Klebsiella pneumoniae), lemon bacterium (Citrobacter) and clostridium butyricum (Clostridium butyricum), the inoculum size of bacterial classification is 5%～20% in the fermenting process, the cell culture apparatus mixing speed is 100～400r/min, temperature is 27～40 ℃, the air flow of nitrogen or air is 0.2～4vvm, the glycerine starting point concentration is 2%～15%, pH is 6.0～8.0, product 1, the concentration of ammediol reaches 10～85g/L; The used film of this technology is the hydrophilic ultra-filtration membrane of asymmetry, and membrane module is flat sheet membrane or hollow-fibre membrane, it is characterized in that:
1) with lipase-catalyzed methyl alcohol or ethanol and the grease reaction generates biofuel and microbial transformation glycerine is 1, two processes of ammediol are got up by the membrane filtration coupling, and two processes are carried out simultaneously;
2) used mould material is organic membrane or inorganic ceramic film, organic membrane refers to polyethersulfone, cellulose ester, polyimide/polyetherimide, polyester fat acid amides and polyacrylonitrile, ceramic membrane is meant pellumina, titanium dioxide film, silicon dioxide film, zirconium dioxide film and composite membrane thereof, and molecular weight cut off is 10～50kDa;
3) working pressure of film is 0.1MPa～0.5Mpa, the film both sides are respectively enzymic catalytic reaction liquid and 1, the ammediol fermented liquid, the high 0.001MPa～0.05Mpa of pressure ratio fermented liquid of reaction solution one side, liquid flow rate is respectively 3.6～7.2h with the ratio of the volume of enzyme reactor and cell culture apparatus -1With 4.8～9.6h -1
4) service temperature of film depends on the temperature of cell cultures, is generally 27～40 ℃, and the temperature of reaction solution one side is higher 0～5 ℃ than fermented liquid one side, when the temperature head of both sides exceeds above-mentioned scope, with placed in-line two interchanger cooling or reacting by heating liquid before and after the film.
CNB2004101004792A 2004-12-23 2004-12-23 Process for coupling producing bioloigical diesel oil and 1,3-propylene glycol Expired - Fee Related CN1276962C (en)

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WO2006089429A1 (en) * 2005-02-28 2006-08-31 University Of Ottawa Apparatus and method for bio-fuel production
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CN108893497A (en) * 2018-07-18 2018-11-27 大连理工大学 A kind of many cells system and fermentation process changing aeration condition regulation product

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