CN103343147A - Method for preparing dibutyl succinate from cassava raw materials - Google Patents
Method for preparing dibutyl succinate from cassava raw materials Download PDFInfo
- Publication number
- CN103343147A CN103343147A CN2013103286186A CN201310328618A CN103343147A CN 103343147 A CN103343147 A CN 103343147A CN 2013103286186 A CN2013103286186 A CN 2013103286186A CN 201310328618 A CN201310328618 A CN 201310328618A CN 103343147 A CN103343147 A CN 103343147A
- Authority
- CN
- China
- Prior art keywords
- succinic acid
- cassava
- reactor
- dibutyl succinate
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention relates to a method for preparing dibutyl succinate from cassava raw materials, which comprises the following steps: pulverizing cassava blocks; liquefying the cassava; saccharifying the cassava; sterilizing a fermentation tank and a material supplementing tank; preparing a fermentation culture medium; sterilizing the fermentation culture medium; performing inoculation fermentation on the culture medium; filtering and decolorizing the fermentation liquid; performing ion exchange on the decolorized fermentation liquid; evaporating to concentrate a succinic acid solution; crystallizing the succinic acid concentrated solution; drying the succinic acid crystals; and preparing the dibutyl succinate. According to the invention, by selecting the reasonable process steps, the non-food crop cassava is subjected to pretreatment; then, a specific strain is selected to ferment the cassava raw material solution to obtain succinic acid; and the succinic acid is further prepared into the dibutyl succinate. In the preparation process, the sugar acid conversion rate is very high, and the cassava is fully utilized almost.
Description
Technical field
The present invention relates to the Succinic Acid preparing technical field, be specifically related to a kind of method by cassava feedstock production dibutyl succinate.
Background technology
Succinic Acid is a kind of very important chemical material, mainly for the preparation of five heterogeneous ring compounds such as succinyl oxides.Also for the preparation of Synolac (Synolac by Succinic Acid production has good flexibility, elasticity and water resisting property), paint, dyestuff (diphenyl of Succinic Acid is the intermediate of dyestuff, generates anthraquinone dye with aminoanthraquinone reaction back), (Succinic Acid also can be done the seasoning that acid condiment is used for wine, feed, candy etc. to food-flavoring comps.), photographic material etc.Anticonvulsants, loose phlegm agent, diuretic(s) and haemostatic medicaments such as available its production sulfa drug, vitamin A, vitamins B in the medicine industry.As chemical reagent, as alkalimetry standard reagent, buffer reagent, gas-chromatography comparative sample.The raw material that also can be used as lubricant and tensio-active agent.
The production of Succinic Acid at present mainly is based on the petrochemical complex route that cis-butenedioic anhydride is raw material.Oil price fluctuates very big in recent years, and this has seriously restricted sustainability and price steadiness that Succinic Acid is produced.On the other hand, chemical synthesis complex process and often need High Temperature High Pressure, this has increased greatly produces required energy consumption material consumption; Chemosynthesis simultaneously also can cause serious environmental to pollute.
Some have also occurred and utilized microbial fermentation to prepare the method for Succinic Acid, but the raw material that is to use mostly is food crop, the cost height, and also productive rate is very low, and effect is not very good, and this also just causes the production cost of dibutyl succinate very high.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method by cassava feedstock production dibutyl succinate, and its cost is low, the productive rate height, thus eliminate defective in the above-mentioned background technology.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of method by cassava feedstock production dibutyl succinate comprises the steps:
The pulverizing of A, cassava piece
Choose high-quality cassava piece, pulverize with sieve sheet aperture Φ 1.5mm pulverizer, be placed in the reactor;
The liquefaction of B, cassava
Add water in the reactor, the weight ratio of water and cassava piece is 2:1～3:1, open and stir, and rotating speed 100～150r/min, power-on is heated to 80～100 ℃;
Adding amylase activity in the reactor is the amylase of 10000U/ml, and the weight ratio of amylase and cassava piece is 1:200～1:150, keeps 80～100 ℃ of constant temperature 0.5～1.5h;
The saccharification of C, cassava
A, off-response kettle heater, open cooling water, the cassava liquefier is down to 55～65 ℃, adding saccharifying enzymic activity is the saccharifying enzyme of 10000U/ml, the weight ratio of saccharifying enzyme and cassava piece is 1:40～1:60, opens the reactor well heater and keeps 55～65 ℃ of constant temperature 1～3h;
B, with cassava saccharification liquid whizzer solid-liquid separation, filter with 100～130 order filter clothes again;
C, measure the glucose quality percentage composition in the filtrate, thin up is to the 18wt% glucose solution;
The sterilization of D, fermentor tank and feed supplement jar
Fermentor tank and feed supplement jar are put into Autoclave carry out 120～140 ℃ of constant temperature sterilization 30～60min;
The preparation of E, fermention medium
| The fermention medium title | Content (g/3L) |
| The cassava Glucose Liquid | 180 |
| Primary ammonium phosphate | 2.75 |
| Secondary ammonium phosphate | 0.48 |
| Magnesium sulfate heptahydrate | 0.85 |
| Repone K | 1.26 |
| Trace metal salts | 4.5 |
| Feed supplement liquid | Content (kg/5L) |
| Sodium hydroxide | 1.54 |
| Yellow soda ash | 2.19 |
The sterilization of F, fermention medium
Fermentation tank culture medium is put into Autoclave carry out 120～140 ℃ of constant temperature sterilization 30～60min;
The inoculation fermentation of G, substratum
Open automatic temperature control system, culture medium after sterilization is down to 37 ℃ and keep temperature constant state;
The fermentor tank rotating speed transfers to 180～230r/min;
With feed supplement liquid medium pH is transferred to 5.6～6.6;
Inoculation bacillus coli gene engineering strain seed liquor, the volume ratio of seed liquor and fermention medium is 1:0～1:110;
Open peristaltic pump, auto-feeding feed supplement liquid, pH are controlled between 6.0～6.2, anaerobically fermenting 72～0h;
Institute's succinic acid-producing is that form with the Succinic Acid sodium salt exists in the fermented liquid;
The filtration of H, fermented liquid and decolouring
Fermented liquid is warming up to 80～90 ℃, keeps 30～60min sterilization;
With the ceramic membrane ultrafitration system fermented liquid is carried out membrane filtration;
Fermented liquid after the ultrafiltration is decoloured with the activated carbon decolorizing post;
The ion-exchange of I, decolouring fermented liquid
Fermented liquid after the decolouring enters cationic resin column and carries out ion-exchange, and the Soduxin in the fermented liquid is changed into Succinic Acid;
The evaporation concentration of J, Succinic Acid solution
To enter the vacuum-evaporation concentration systems from the Succinic Acid solution after handing over and be concentrated into 200g/l, 40～50 ℃ of solution temperatures;
The crystallization of K, Succinic Acid concentrated solution
The Succinic Acid concentrated solution is cooled to 20 ℃, and the Succinic Acid crystallization is separated out;
Mother liquor behind the primary crystallization concentrates again, carries out secondary crystal and separates out;
Mother liquor behind the secondary crystal concentrates again, carries out three crystallizations and separates out;
The drying of L, Succinic Acid xln
The Succinic Acid crystal that crystallization is separated out carries out vacuum-drying, obtains qualified Succinic Acid solid;
M, Succinic Acid solid and the butanols of the preparation esterifying catalyst mole when by 1:2～6 is joined in the reactor;
N, be under 100～150 ℃ in temperature of reaction, make Succinic Acid and butanols generation esterification in the reactor, the reaction times is 3～9h, generation Succinic Acid butyl ester and water;
After O, reactor internal reaction finished, product was sent in the rectifying tower in the still, removes the moisture in the product, and the product at the bottom of the tower is succinate, comprises dibutyl succinate and Succinic Acid mono;
The bottom product of P, rectifying tower is sent into the catalytic rectifying tower rectifying section, the catalytic rectifying tower processing condition are: pressure 0.1～0.5MPa, 120～180 ℃ of tower reactor temperature, 90～120 ℃ of tower top temperatures, the catalytic rectifying tower stripping section is pressed rectifying section charging succinate mol ratio 1:1～5 input butanols simultaneously;
Q, the discharging of catalytic distillation column overhead are butanols and water, take out described dibutyl succinate at the bottom of tower.
As a kind of improvement, fermented bacterium is succinic acid-producing bacillus coli gene engineering strain, and preserving number is: CGMCC No.4512.
As a kind of improvement, in the described ceramic membrane ultrafitration system, the ceramic membrane aperture is 50nm.
As a kind of improvement, adopt 732 type Zeo-karbs in the described cationic resin column.
As a kind of improvement, described catalytic rectifying tower is a kind of chemical industry equipment that esterification and rectifying are coupled.That is to say that the bottom of this catalytic rectifying tower is the catalytic esterification tower body, top is coupled with rectifying tower.
Among the present invention, institute's succinic acid-producing is that form with the Succinic Acid sodium salt exists in the fermented liquid, and molecular weight is that 118 Succinic Acid concentration reaches 110g/l, glucose acid invert ratio 0.95～1.05g/g.
Among the present invention, fermention medium is minimal medium.
Among the present invention, feed supplement liquid is the mixing solutions of sodium hydroxide and yellow soda ash, and its mass ratio is 0.7:1.
Utilize finished product Succinic Acid purity that the present invention produces greater than 99.5%, yield is greater than 92%.
Among the present invention, the dibutyl succinate that takes out at the bottom of the described catalytic distillation Tata, impurity is considerably less, quality percentage composition 〉=99.5% of dibutyl succinate, Succinic Acid mono≤0.1%.
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
The present invention has adopted cassava as raw material, cassava is different from traditional food crop such as corn, wheat, cheap, belong to renewable resources, and starch content is very high in the cassava, the present invention adopts non-grain raw material to utilize biological fermentation process to prepare Succinic Acid, has reduced environmental pollution, more meets national existing policy.
Among the present invention, at first with the pulverizing of cassava piece, liquefaction, saccharification, utilize sieve sheet aperture Φ 1.5mm pulverizer to pulverize during pulverizing, during liquefaction, the weight ratio of water and cassava piece is 2:1～3:1, open and stir, rotating speed 100～150r/min, power-on is heated to 80～100 ℃, and adding amylase activity in the reactor is the amylase of 10000U/ml, the weight ratio of amylase and cassava piece is 1:200～1:150, keeps 80～100 ℃ of constant temperature 0.5～1.5h; During saccharification, the cassava liquefier is down to 55～65 ℃, adding saccharifying enzymic activity is the saccharifying enzyme of 10000U/ml, the weight ratio of saccharifying enzyme and cassava piece is 1:40～1:60, keep 55～65 ℃ of constant temperature 1～3h, use the whizzer solid-liquid separation, filter with 100～130 order filter clothes again.More than be that the contriver is after the prolonged and repeated experiment of process, the processing step of formulating at this specific non-grain raw material of cassava, in fact, when utilizing above-mentioned steps that cassava is handled, can be with the abundant saccharification of the starch in the cassava, the starch transformation efficiency is more than 98%.The contriver also attempted other traditional methods, for example change some step or processing parameter in the above-mentioned technology, but effect was all undesirable, and in experiment, when not adopting above-mentioned technology, the starch transformation efficiency is up to 90% in the cassava.As seen, during to the processing of cassava, adopt above-mentioned steps, reached very significant effect.
The present invention has adopted special bacterial classification, is colon bacillus (Escherichia coli) XZT124, and preserving number is CGMCC No.4512, and according to the characteristics of cassava, in conjunction with the characteristic of bacterial classification, after testing repeatedly in a large number, selected an operational path that meets suitability for industrialized production more.In the fermention medium in early stage, contain cassava Glucose Liquid, primary ammonium phosphate, Secondary ammonium phosphate, magnesium sulfate heptahydrate, Repone K, trace metal salts, not only can make bacterial classification just can adapt to cassava raw material environment early stage, and enough inorganic salt and other material can be provided; In addition, designed the pH that feed supplement liquid is used for adjusting substratum, when formal fermentation, inoculation bacillus coli gene engineering strain seed liquor, the volume ratio of seed liquor and fermention medium is 1:90～1:110, opens peristaltic pump, auto-feeding feed supplement liquid, pH controls between 6.0～6.2, anaerobically fermenting 72～80h.Institute's succinic acid-producing is that form with the Succinic Acid sodium salt exists in the fermented liquid that obtains, molecular weight is that 118 Succinic Acid concentration reaches 110g/l, repeatedly sampling and measuring through the contriver is calculated, and finds that the theoretical maximum of glucose acid invert ratio 0.95～1.05g/g(is 1.12g/g).That is to say, adopt specific bacterial classification among the present invention, specific technology, the cassava raw material is fermented, played the effect of highly significant.
The present invention also adopts specific technology that fermented liquid is carried out aftertreatment, to obtain qualified Succinic Acid crystal, at first sterilization, with the ceramic membrane ultrafitration system fermented liquid is carried out membrane filtration, the fermented liquid after the ultrafiltration is decoloured with the activated carbon decolorizing post, enter cationic resin column then and carry out ion-exchange, adopt the vacuum-evaporation concentration systems to be concentrated into 200g/l, 40～50 ℃ of solution temperatures adopt three crystallizations at last, obtain qualified Succinic Acid solid after the vacuum-drying.In the aftertreatment, do not introduce other impurity, guaranteed the purity of Succinic Acid.
The present invention is directed to the Succinic Acid that utilizes cassava to produce, designed rational step, adopt earlier pre-esterification, rectifying again, enter catalytic rectifying tower then and carry out degree of depth esterification method, the dibutyl succinate impurity of final production is considerably less, quality percentage composition 〉=99.5% of dibutyl succinate, Succinic Acid mono≤0.1%.
In a word, most important significance of the present invention is, has selected rational processing step, and non-grain crop-cassava is carried out pre-treatment, select specific bacterial classification then for use, the cassava stock liquid is fermented, make Succinic Acid, and in the preparation process, glucose acid invert ratio is very high, and is more complete to the utilization of cassava.
Be compared to traditional food crop such as corn, wheat, cost of the present invention is lower.Under the identical situation of glucose acid invert ratio, the present invention produces Succinic Acid cost per ton at 6000～7000 yuan, and utilizes Maize Production Succinic Acid cost per ton about 10000 yuan, and is high by about 40%.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
A kind of method by cassava feedstock production dibutyl succinate, adopt following steps:
The pulverizing of A, cassava piece
Choose high-quality cassava piece, pulverize with sieve sheet aperture Φ 1.5mm pulverizer, be placed in the reactor;
The liquefaction of B, cassava
Add water in the reactor, the weight ratio of water and cassava piece is 2:1, open and stir, and rotating speed 100r/min, power-on is heated to 80 ℃;
Adding amylase activity in the reactor is the amylase of 10000U/ml, and the weight ratio of amylase and cassava piece is 1:200, keeps 80 ℃ of constant temperature 0.5h;
The saccharification of C, cassava
A, off-response kettle heater are opened cooling water, and the cassava liquefier is down to 55 ℃, and adding saccharifying enzymic activity is the saccharifying enzyme of 10000U/ml, and the weight ratio of saccharifying enzyme and cassava piece is 1:40, open the reactor well heater and keep 55 ℃ of constant temperature 1h;
B, with cassava saccharification liquid whizzer solid-liquid separation, filter with 100 order filter clothes again;
C, measure the glucose quality percentage composition in the filtrate, thin up is to the 18wt% glucose solution;
The sterilization of D, fermentor tank and feed supplement jar
Fermentor tank and feed supplement jar are put into Autoclave carry out 120～140 ℃ of constant temperature sterilization 30～60min;
The preparation of E, fermention medium
| The fermention medium title | Content (g/3L) |
| The cassava Glucose Liquid | 180 |
| Primary ammonium phosphate | 2.75 |
| Secondary ammonium phosphate | 0.48 |
| Magnesium sulfate heptahydrate | 0.85 |
| Repone K | 1.26 |
| Trace metal salts | 4.5 |
| Feed supplement liquid | Content (kg/5L) |
| Sodium hydroxide | 1.54 |
| Yellow soda ash | 2.19 |
The sterilization of F, fermention medium
Fermentation tank culture medium is put into Autoclave carry out 120 ℃ of constant temperature sterilization 30min;
The inoculation fermentation of G, substratum
Open automatic temperature control system, culture medium after sterilization is down to 37 ℃ and keep temperature constant state;
The fermentor tank rotating speed transfers to 180r/min;
With feed supplement liquid medium pH is transferred to 5.6;
Adopting fermented bacterium is succinic acid-producing bacillus coli gene engineering strain, and preserving number is: CGMCC No.4512; Inoculation bacillus coli gene engineering strain seed liquor, the volume ratio of seed liquor and fermention medium is 1:90;
Open peristaltic pump, auto-feeding feed supplement liquid, pH controls 6.0, anaerobically fermenting 72h;
Institute's succinic acid-producing is that form with the Succinic Acid sodium salt exists in the fermented liquid; Molecular weight is that 118 Succinic Acid concentration reaches 110g/l, glucose acid invert ratio 0.95～1.05g/g.
The filtration of H, fermented liquid and decolouring
Fermented liquid is warming up to 80 ℃, keeps the 30min sterilization;
With the ceramic membrane ultrafitration system fermented liquid is carried out membrane filtration, in the described ceramic membrane ultrafitration system, the ceramic membrane aperture is 50nm;
Fermented liquid after the ultrafiltration is decoloured with the activated carbon decolorizing post;
The ion-exchange of I, decolouring fermented liquid
Fermented liquid after the decolouring enters cationic resin column and carries out ion-exchange, and the Soduxin in the fermented liquid is changed into Succinic Acid, adopts 732 type Zeo-karbs in the described cationic resin column;
The evaporation concentration of J, Succinic Acid solution
To enter the vacuum-evaporation concentration systems from the Succinic Acid solution after handing over and be concentrated into 200g/l, 40～50 ℃ of solution temperatures;
The crystallization of K, Succinic Acid concentrated solution
The Succinic Acid concentrated solution is cooled to 20 ℃, and the Succinic Acid crystallization is separated out;
Mother liquor behind the primary crystallization concentrates again, carries out secondary crystal and separates out;
Mother liquor behind the secondary crystal concentrates again, carries out three crystallizations and separates out;
The drying of L, Succinic Acid xln
The Succinic Acid crystal that crystallization is separated out carries out vacuum-drying, obtains qualified Succinic Acid solid;
M, Succinic Acid solid and the butanols of the preparation esterifying catalyst mole when by 1:2 is joined in the reactor;
N, be under 100 ℃ in temperature of reaction, make Succinic Acid and butanols generation esterification in the reactor, the reaction times is 3h, generation Succinic Acid butyl ester and water;
After O, reactor internal reaction finished, product was sent in the rectifying tower in the still, removes the moisture in the product, and the product at the bottom of the tower is succinate, comprises dibutyl succinate and Succinic Acid mono;
The bottom product of P, rectifying tower is sent into the catalytic rectifying tower rectifying section, and the catalytic rectifying tower processing condition are: pressure 0.1MPa, and 120 ℃ of tower reactor temperature, 90 ℃ of tower top temperatures, the catalytic rectifying tower stripping section is pressed rectifying section charging succinate mol ratio 1:5 input butanols simultaneously;
Q, the discharging of catalytic distillation column overhead are butanols and water, take out described dibutyl succinate at the bottom of tower.
The contriver utilizes 1.6 tons cassava raw material in strict accordance with above processing parameter, prepares 1100 kilograms Succinic Acid solid, and output is than being 1:0.69; And then prepare the 2057kg dibutyl succinate, the purity that obtains dibutyl succinate after testing is 99.5%.
Embodiment 2
A kind of method by cassava feedstock production dibutyl succinate comprises the steps:
The pulverizing of A, cassava piece
Choose high-quality cassava piece, pulverize with sieve sheet aperture Φ 1.5mm pulverizer, be placed in the reactor;
The liquefaction of B, cassava
Add water in the reactor, the weight ratio of water and cassava piece is 2.5:1, open and stir, and rotating speed 120r/min, power-on is heated to 90 ℃;
Adding amylase activity in the reactor is the amylase of 10000U/ml, and the weight ratio of amylase and cassava piece is 1:170, keeps 90 ℃ of constant temperature 1.0h;
The saccharification of C, cassava
A, off-response kettle heater are opened cooling water, and the cassava liquefier is down to 60 ℃, and adding saccharifying enzymic activity is the saccharifying enzyme of 10000U/ml, and the weight ratio of saccharifying enzyme and cassava piece is 1:50, open the reactor well heater and keep 60 ℃ of constant temperature 1～3h;
B, with cassava saccharification liquid whizzer solid-liquid separation, filter with 120 order filter clothes again;
C, measure the glucose quality percentage composition in the filtrate, thin up is to the 18wt% glucose solution;
The sterilization of D, fermentor tank and feed supplement jar
Fermentor tank and feed supplement jar are put into Autoclave carry out 130 ℃ of constant temperature sterilization 45min;
The preparation of E, fermention medium
| The fermention medium title | Content (g/3L) |
| The cassava Glucose Liquid | 180 |
| Primary ammonium phosphate | 2.75 |
| Secondary ammonium phosphate | 0.48 |
| Magnesium sulfate heptahydrate | 0.85 |
| Repone K | 1.26 |
| Trace metal salts | 4.5 |
| Feed supplement liquid | Content (kg/5L) |
| Sodium hydroxide | 1.54 |
| Yellow soda ash | 2.19 |
The sterilization of F, fermention medium
Fermentation tank culture medium is put into Autoclave carry out 130 ℃ of constant temperature sterilization 45min;
The inoculation fermentation of G, substratum
Open automatic temperature control system, culture medium after sterilization is down to 37 ℃ and keep temperature constant state;
The fermentor tank rotating speed transfers to 200r/min;
With feed supplement liquid medium pH is transferred to 6.0;
Adopting fermented bacterium is succinic acid-producing bacillus coli gene engineering strain, and preserving number is: CGMCCNo.4512; Inoculation bacillus coli gene engineering strain seed liquor, the volume ratio of seed liquor and fermention medium is 1:100;
Open peristaltic pump, auto-feeding feed supplement liquid, pH controls 6.1, anaerobically fermenting 75h;
Institute's succinic acid-producing is that form with the Succinic Acid sodium salt exists in the fermented liquid; Molecular weight is that 118 Succinic Acid concentration reaches 110g/l, glucose acid invert ratio 1.05g/g.
The filtration of H, fermented liquid and decolouring
Fermented liquid is warming up to 85 ℃, keeps the 45min sterilization;
With the ceramic membrane ultrafitration system fermented liquid is carried out membrane filtration, in the described ceramic membrane ultrafitration system, the ceramic membrane aperture is 50nm;
Fermented liquid after the ultrafiltration is decoloured with the activated carbon decolorizing post;
The ion-exchange of I, decolouring fermented liquid
Fermented liquid after the decolouring enters cationic resin column and carries out ion-exchange, and the Soduxin in the fermented liquid is changed into Succinic Acid, adopts 732 type Zeo-karbs in the described cationic resin column;
The evaporation concentration of J, Succinic Acid solution
To enter the vacuum-evaporation concentration systems from the Succinic Acid solution after handing over and be concentrated into 200g/l, 45 ℃ of solution temperatures;
The crystallization of K, Succinic Acid concentrated solution
The Succinic Acid concentrated solution is cooled to 20 ℃, and the Succinic Acid crystallization is separated out;
Mother liquor behind the primary crystallization concentrates again, carries out secondary crystal and separates out;
Mother liquor behind the secondary crystal concentrates again, carries out three crystallizations and separates out;
The drying of L, Succinic Acid xln
The Succinic Acid crystal that crystallization is separated out carries out vacuum-drying, obtains qualified Succinic Acid solid;
M, Succinic Acid solid and the butanols of the preparation esterifying catalyst mole when by 1:6 is joined in the reactor;
N, be under 150 ℃ in temperature of reaction, make Succinic Acid and butanols generation esterification in the reactor, the reaction times is 9h, generation Succinic Acid butyl ester and water;
After O, reactor internal reaction finished, product was sent in the rectifying tower in the still, removes the moisture in the product, and the product at the bottom of the tower is succinate, comprises dibutyl succinate and Succinic Acid mono;
The bottom product of P, rectifying tower is sent into the catalytic rectifying tower rectifying section, the catalytic rectifying tower processing condition are: pressure 0.3MPa, 150 ℃ of tower reactor temperature, 105 ℃ of tower top temperatures, the catalytic rectifying tower stripping section is pressed rectifying section charging succinate mol ratio 1:3 input butanols simultaneously;
Q, the discharging of catalytic distillation column overhead are butanols and water, take out described dibutyl succinate at the bottom of tower.
The contriver utilizes 1.6 tons cassava raw material in strict accordance with above processing parameter, prepares 1200 kilograms Succinic Acid solid, and output is than being 1:0.75; And then prepare the 2295kg dibutyl succinate, detect and find: finished product Succinic Acid purity is 99.8%; The purity of dibutyl succinate is 99.8%.
Embodiment 3
A kind of method by cassava feedstock production dibutyl succinate comprises the steps:
The pulverizing of A, cassava piece
Choose high-quality cassava piece, pulverize with sieve sheet aperture Φ 1.5mm pulverizer, be placed in the reactor;
The liquefaction of B, cassava
Add water in the reactor, the weight ratio of water and cassava piece is 3:1, open and stir, and rotating speed 150r/min, power-on is heated to 100 ℃;
Adding amylase activity in the reactor is the amylase of 10000U/ml, and the weight ratio of amylase and cassava piece is 1:150, keeps 100 ℃ of constant temperature 1.5h;
The saccharification of C, cassava
A, off-response kettle heater are opened cooling water, and the cassava liquefier is down to 65 ℃, and adding saccharifying enzymic activity is the saccharifying enzyme of 10000U/ml, and the weight ratio of saccharifying enzyme and cassava piece is 1:60, open the reactor well heater and keep 65 ℃ of constant temperature 3h;
B, with cassava saccharification liquid whizzer solid-liquid separation, filter with 130 order filter clothes again;
C, measure the glucose quality percentage composition in the filtrate, thin up is to the 18wt% glucose solution;
The sterilization of D, fermentor tank and feed supplement jar
Fermentor tank and feed supplement jar are put into Autoclave carry out 140 ℃ of constant temperature sterilization 60min;
The preparation of E, fermention medium
| The fermention medium title | Content (g/3L) |
| The cassava Glucose Liquid | 180 |
| Primary ammonium phosphate | 2.75 |
| Secondary ammonium phosphate | 0.48 |
| Magnesium sulfate heptahydrate | 0.85 |
| Repone K | 1.26 |
| Trace metal salts | 4.5 |
| Feed supplement liquid | Content (kg/5L) |
| Sodium hydroxide | 1.54 |
| Yellow soda ash | 2.19 |
The sterilization of F, fermention medium
Fermentation tank culture medium is put into Autoclave carry out 140 ℃ of constant temperature sterilization 60min;
The inoculation fermentation of G, substratum
Open automatic temperature control system, culture medium after sterilization is down to 37 ℃ and keep temperature constant state;
The fermentor tank rotating speed transfers to 230r/min;
With feed supplement liquid medium pH is transferred to 6.6;
Inoculation bacillus coli gene engineering strain seed liquor, the volume ratio of seed liquor and fermention medium is 1:110;
Open peristaltic pump, auto-feeding feed supplement liquid, pH controls 6.2, anaerobically fermenting 80h;
Institute's succinic acid-producing is that form with the Succinic Acid sodium salt exists in the fermented liquid; Molecular weight is that 118 Succinic Acid concentration reaches 110g/l, glucose acid invert ratio 0.95～1.05g/g.
The filtration of H, fermented liquid and decolouring
Fermented liquid is warming up to 90 ℃, keeps the 60min sterilization;
With the ceramic membrane ultrafitration system fermented liquid is carried out membrane filtration, in the described ceramic membrane ultrafitration system, the ceramic membrane aperture is 50nm;
Fermented liquid after the ultrafiltration is decoloured with the activated carbon decolorizing post;
The ion-exchange of I, decolouring fermented liquid
Fermented liquid after the decolouring enters cationic resin column and carries out ion-exchange, and the Soduxin in the fermented liquid is changed into Succinic Acid, adopts 732 type Zeo-karbs in the described cationic resin column;
The evaporation concentration of J, Succinic Acid solution
To enter the vacuum-evaporation concentration systems from the Succinic Acid solution after handing over and be concentrated into 200g/l, 50 ℃ of solution temperatures;
The crystallization of K, Succinic Acid concentrated solution
The Succinic Acid concentrated solution is cooled to 20 ℃, and the Succinic Acid crystallization is separated out;
Mother liquor behind the primary crystallization concentrates again, carries out secondary crystal and separates out;
Mother liquor behind the secondary crystal concentrates again, carries out three crystallizations and separates out;
The drying of L, Succinic Acid xln
The Succinic Acid crystal that crystallization is separated out carries out vacuum-drying, obtains qualified Succinic Acid solid;
M, Succinic Acid solid and the butanols of the preparation esterifying catalyst mole when by 1:4 is joined in the reactor;
N, be under 120 ℃ in temperature of reaction, make Succinic Acid and butanols generation esterification in the reactor, the reaction times is 7h, generation Succinic Acid butyl ester and water;
After O, reactor internal reaction finished, product was sent in the rectifying tower in the still, removes the moisture in the product, and the product at the bottom of the tower is succinate, comprises dibutyl succinate and Succinic Acid mono;
The bottom product of P, rectifying tower is sent into the catalytic rectifying tower rectifying section, the catalytic rectifying tower processing condition are: pressure 0.5MPa, 180 ℃ of tower reactor temperature, 120 ℃ of tower top temperatures, the catalytic rectifying tower stripping section is pressed rectifying section charging succinate mol ratio 1:3 input butanols simultaneously;
Q, the discharging of catalytic distillation column overhead are butanols and water, take out described dibutyl succinate at the bottom of tower.
The contriver utilizes 1.6 tons cassava raw material in strict accordance with above processing parameter, prepares 1136 kilograms Succinic Acid solid, and the output ratio is 1:0.7, and then prepares the 1987kg dibutyl succinate, and detect and find: finished product Succinic Acid purity is 99.5%; The purity of dibutyl succinate is 99.6%.
From above-described embodiment also as can be seen, when in strict accordance with the step of embodiment 2, the output of Succinic Acid solid of the present invention is than the highest, apparently higher than embodiment 1 and embodiment 3.
The comparative example 1
Owing to do not utilize at present biological fermentation process to produce the write up of Succinic Acid, therefore, comparative example 1 adopts the step identical with embodiment 2.
Difference is that this comparative example utilizes the food crop corn as raw material, and bacterial classification adopts traditional natural succinic acid-producing bacterium.
The result is as follows:
Raw material is the 100kg corn, and the Succinic Acid solid masses of output is 63kg, and output is than being 1:0.63; The purity of Succinic Acid solid is 99.5%.
As seen, when utilizing corn as raw material, with respect to cassava as for the raw material, output is lower than very.And cost is very high.The contriver compares other food crop such as wheats simultaneously, as a result unanimity.
The comparative example 2
Be raw material with the corn, step is in strict accordance with the step of embodiment 2, and bacterial classification adopts bacterial classification provided by the invention.
The result is as follows:
Raw material is the 100kg corn, and the Succinic Acid solid masses of output is 64kg, and output is than being 1:0.64; The purity of Succinic Acid solid is 99.5%.
As seen, with respect to cassava as for the raw material, even if adopt under the situation of identical bacterial classification, when utilizing corn as raw material, the output of Succinic Acid is very lower than still, and cost is very high.The contriver compares other food crop such as wheats simultaneously, as a result unanimity.
The comparative example 3
Be raw material with the cassava, but pre-treatment step is different from embodiment 1,2,3, but adopts conventional pulverizing, add enzyme and decompose, in strict accordance with the step among the embodiment 2 its glucose solution is fermented again after generating glucose solution.
The result is as follows:
Raw material is the 100kg cassava, and the Succinic Acid solid masses of output is 64kg, and output is than being 1:0.64; The purity of Succinic Acid solid is 99.5%.
As seen, when not adopting cassava pre-treating technology provided by the invention, the output of Succinic Acid is than also corresponding minimizing.Pre-treatment step of the present invention is very big to the yield effect of later stage Succinic Acid solid.
The comparative example 4
Be raw material with the cassava, carry out in strict accordance with the step that embodiment 2 provides that difference is to have adopted traditional natural succinic acid-producing bacterium as bacterial classification, and fermentation condition is chosen as the optimal conditions of this bacterial classification.
The result is as follows:
Raw material is the 100kg cassava, and the Succinic Acid solid masses of output is 59kg, and output is than being 1:0.59; The purity of Succinic Acid solid is 99.5%.
As seen, when not adopting cassava pre-treating technology provided by the invention, the output ratio of Succinic Acid significantly reduces.When adopting cassava to be raw material, adopt specific bacterial classification very big to the yield effect of Succinic Acid solid.
The comparative example 5
Be raw material with the cassava, step is in strict accordance with the step of embodiment 2, and bacterial classification adopts bacterial classification provided by the invention.Difference is, obtain the Succinic Acid solid after, adopts traditional dibutyl succinate preparation method, be about to the Succinic Acid solid directly and butanols reacts, both mol ratios are 1:3～6.
The result is as follows:
Raw material is the 100kg cassava, and the Succinic Acid solid masses of output is 74kg, and output is than being 1:0.74; And the dibutyl succinate quality that makes is only for 103kg, and the purity of dibutyl succinate only is 85.3%, and wherein the massfraction of Succinic Acid mono is up to 11.3%, and all the other are other impurity.
As seen, do not adopt follow-up esterification process provided by the invention, even if adopt cassava to prepare high yield, highly purified Succinic Acid solid according to the step before the present invention, the quality of later stage dibutyl succinate also can't be protected.
The present invention is not limited to above-mentioned embodiment, and all are based on technical conceive of the present invention, and the structural improvement of having done all falls among protection scope of the present invention.
Claims (5)
1. the method by cassava feedstock production dibutyl succinate is characterized in that: comprise the steps:
The pulverizing of A, cassava piece
Choose high-quality cassava piece, pulverize with sieve sheet aperture Φ 1.5mm pulverizer, be placed in the reactor;
The liquefaction of B, cassava
Add water in the reactor, the weight ratio of water and cassava piece is 2:1～3:1, opens and stirs, and rotating speed 100～150r/min is heated to 80～100 ℃;
Adding amylase activity in the reactor is the amylase of 10000U/ml, and the weight ratio of amylase and cassava piece is 1:200～1:150, keeps 80～100 ℃ of constant temperature 0.5～1.5h;
The saccharification of C, cassava
A, off-response kettle heater, open cooling water, the cassava liquefier is down to 55～65 ℃, adding saccharifying enzymic activity is the saccharifying enzyme of 10000U/ml, the weight ratio of saccharifying enzyme and cassava piece is 1:40～1:60, opens the reactor well heater and keeps 55～65 ℃ of constant temperature 1～3h;
B, with cassava saccharification liquid whizzer solid-liquid separation, filter with 100～130 order filter clothes again;
C, measure the glucose quality percentage composition in the filtrate, thin up is to the 18wt% glucose solution;
The sterilization of D, fermentor tank and feed supplement jar
Fermentor tank and feed supplement jar are put into Autoclave carry out 120～140 ℃ of constant temperature sterilization 30～60min;
The preparation of E, fermention medium
The sterilization of F, fermention medium
Fermentation tank culture medium is put into Autoclave carry out 120～140 ℃ of constant temperature sterilization 30～60min;
The inoculation fermentation of G, substratum
Open automatic temperature control system, culture medium after sterilization is down to 37 ℃ and keep temperature constant state;
The fermentor tank rotating speed transfers to 180～230r/min;
With feed supplement liquid medium pH is transferred to 5.6～6.6;
Inoculation bacillus coli gene engineering strain seed liquor, the volume ratio of seed liquor and fermention medium is 1:90～1:110;
Open peristaltic pump, auto-feeding feed supplement liquid, pH are controlled between 6.0～6.2, anaerobically fermenting 72～80h;
The filtration of H, fermented liquid and decolouring
Fermented liquid is warming up to 80～90 ℃, keeps 30～60min sterilization;
With the ceramic membrane ultrafitration system fermented liquid is carried out membrane filtration;
Fermented liquid after the ultrafiltration is decoloured with the activated carbon decolorizing post;
The ion-exchange of I, decolouring fermented liquid
Fermented liquid after the decolouring enters cationic resin column and carries out ion-exchange, and the Soduxin in the fermented liquid is changed into Succinic Acid;
The evaporation concentration of J, Succinic Acid solution
To enter the vacuum-evaporation concentration systems from the Succinic Acid solution after handing over and be concentrated into 200g/l, 40～50 ℃ of solution temperatures;
The crystallization of K, Succinic Acid concentrated solution
The Succinic Acid concentrated solution is cooled to 20 ℃, and the Succinic Acid crystallization is separated out;
Mother liquor behind the primary crystallization concentrates again, carries out secondary crystal and separates out;
Mother liquor behind the secondary crystal concentrates again, carries out three crystallizations and separates out;
The drying of L, Succinic Acid xln
The Succinic Acid crystal that crystallization is separated out carries out vacuum-drying, obtains qualified Succinic Acid solid;
M, Succinic Acid solid and the butanols of the preparation esterifying catalyst mole when by 1:2～6 is joined in the reactor;
N, be under 100～150 ℃ in temperature of reaction, make Succinic Acid and butanols generation esterification in the reactor, the reaction times is 3～9h, generation Succinic Acid butyl ester and water;
After O, reactor internal reaction finished, product was sent in the rectifying tower in the still, removes the moisture in the product, and the product at the bottom of the tower is succinate, comprises dibutyl succinate and Succinic Acid mono;
The bottom product of P, rectifying tower is sent into the catalytic rectifying tower rectifying section, the catalytic rectifying tower processing condition are: pressure 0.1～0.5MPa, 120～180 ℃ of tower reactor temperature, 90～120 ℃ of tower top temperatures, the catalytic rectifying tower stripping section is pressed rectifying section charging succinate mol ratio 1:1～5 input butanols simultaneously;
Q, the discharging of catalytic distillation column overhead are butanols and water, take out described dibutyl succinate at the bottom of tower.
2. a kind of method by cassava feedstock production dibutyl succinate as claimed in claim 1, it is characterized in that: described fermented bacterium is succinic acid-producing bacillus coli gene engineering strain, and preserving number is: CGMCC No.4512.
3. a kind of method by cassava feedstock production dibutyl succinate as claimed in claim 1 is characterized in that: in the described ceramic membrane ultrafitration system, the ceramic membrane aperture is 50nm.
4. a kind of method by cassava feedstock production dibutyl succinate as claimed in claim 1 is characterized in that: adopt 732 type Zeo-karbs in the described cationic resin column.
5. a kind of method by cassava feedstock production dibutyl succinate as claimed in claim 1 is characterized in that: described catalytic rectifying tower is a kind of equipment that esterification and rectifying are coupled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310328618.6A CN103343147B (en) | 2013-07-31 | 2013-07-31 | Method for preparing dibutyl succinate from cassava raw materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310328618.6A CN103343147B (en) | 2013-07-31 | 2013-07-31 | Method for preparing dibutyl succinate from cassava raw materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103343147A true CN103343147A (en) | 2013-10-09 |
| CN103343147B CN103343147B (en) | 2014-12-31 |
Family
ID=49277973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310328618.6A Active CN103343147B (en) | 2013-07-31 | 2013-07-31 | Method for preparing dibutyl succinate from cassava raw materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103343147B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554279A (en) * | 2015-09-28 | 2017-04-05 | 中国石化扬子石油化工有限公司 | A kind of method that succinate is extracted from succinic acid fermentation liquor |
| CN108101744A (en) * | 2017-12-14 | 2018-06-01 | 姜均 | Inositol extraction method |
| CN108721934A (en) * | 2018-08-16 | 2018-11-02 | 青海黄河上游水电开发有限责任公司新能源分公司 | The overall process autocontrol method and system of rectifying column |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067046A (en) * | 1992-01-15 | 1992-12-16 | 黄玉龙 | Method for extracting dicarboxylic acid and esters thereof from adipic acid production waste liquid |
| CN101348429A (en) * | 2008-09-05 | 2009-01-21 | 江南大学 | Method for extracting amber acid in fermentation liquor by cationic resin exchange |
| US20090264674A1 (en) * | 2008-04-17 | 2009-10-22 | National Taiwan University | System and method for producing diester |
| CN102174455A (en) * | 2011-01-28 | 2011-09-07 | 天津工业生物技术研究所 | Escherichia coli genetic engineering bacteria for producing succinic acid and construction method as well as application thereof |
-
2013
- 2013-07-31 CN CN201310328618.6A patent/CN103343147B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067046A (en) * | 1992-01-15 | 1992-12-16 | 黄玉龙 | Method for extracting dicarboxylic acid and esters thereof from adipic acid production waste liquid |
| US20090264674A1 (en) * | 2008-04-17 | 2009-10-22 | National Taiwan University | System and method for producing diester |
| CN101348429A (en) * | 2008-09-05 | 2009-01-21 | 江南大学 | Method for extracting amber acid in fermentation liquor by cationic resin exchange |
| CN102174455A (en) * | 2011-01-28 | 2011-09-07 | 天津工业生物技术研究所 | Escherichia coli genetic engineering bacteria for producing succinic acid and construction method as well as application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张敏: "利用木薯淀粉为原料发酵生产丁二酸的研究", 《中国酿造》 * |
| 谢晓鹏等: "NaHSO4•SiO2 催化合成二元脂肪酸酯", 《有机化学》 * |
| 谢晓鹏等: "NaHSO4•SiO2 催化合成二元脂肪酸酯", 《有机化学》, vol. 30, no. 10, 15 October 2010 (2010-10-15), pages 1512 - 1516 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554279A (en) * | 2015-09-28 | 2017-04-05 | 中国石化扬子石油化工有限公司 | A kind of method that succinate is extracted from succinic acid fermentation liquor |
| CN106554279B (en) * | 2015-09-28 | 2018-12-11 | 中国石化扬子石油化工有限公司 | A method of extracting succinate from succinic acid fermentation liquor |
| CN108101744A (en) * | 2017-12-14 | 2018-06-01 | 姜均 | Inositol extraction method |
| CN108101744B (en) * | 2017-12-14 | 2018-12-11 | 四川安益生物科技有限公司 | Inositol extraction method |
| CN108721934A (en) * | 2018-08-16 | 2018-11-02 | 青海黄河上游水电开发有限责任公司新能源分公司 | The overall process autocontrol method and system of rectifying column |
| CN108721934B (en) * | 2018-08-16 | 2024-04-12 | 青海黄河上游水电开发有限责任公司新能源分公司 | Full-process automatic control method and system for rectifying tower |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103343147B (en) | 2014-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101358218B (en) | Method for producing xylose coupled cogeneration of propanone, butanol and ethanol using stalk | |
| CN102115764B (en) | Method for producing alcohol by taking anaerobic effluent as ingredient water | |
| CN103361385B (en) | Technology for preparation of succinic acid finished product by bioconversion of cassava raw material | |
| CN101070549A (en) | Mixed raw-material fermenting process for producing alcohol | |
| CN102703520B (en) | Method for producing ethanol through mixed fermentation of bagasse hydrolyzate and molasses | |
| WO2016173262A1 (en) | Method for producing cellulosic ethanol by fermenting agricultural and forest biomass waste thick mash | |
| CN103343147B (en) | Method for preparing dibutyl succinate from cassava raw materials | |
| CN104830918A (en) | Novel production method of sodium gluconate | |
| CN102676605A (en) | Method for producing xylose and L-arabinose using xylose mother liquor | |
| CN102250964A (en) | Production technology of starchiness raw material alcohol | |
| CN101878308B (en) | A process for the preparation of ethanol from starch | |
| CN103789354A (en) | Method for preparing ethanol from cellulose-containing raw material | |
| CN105586368B (en) | A kind of method of the processing method and fermentation production of citric acid of sorghum seed | |
| CN104651416A (en) | Method for synchronously producing biological butanol and nano cellulose from sweet sorghum | |
| CN106893682B (en) | Method for expanding culture of saccharomycetes by using liquefied mash and application of saccharomycetes and method for fermenting ethanol | |
| CN101696429B (en) | Method for producing butanol by hydrolyzing and fermenting waste crops rich in hemicellulose | |
| CN106337066B (en) | Process for producing sodium gluconate by energy-saving environment-friendly enzyme method | |
| CN105154494B (en) | A kind of method that lignocellulosic continuous enzymolysis mentions high glucose concentration | |
| CN114617189A (en) | Method for preparing compound protein feed by utilizing cassava vinasse liquid | |
| CN105624219A (en) | Method for producing citric acid by fermenting wheat starch milk | |
| CN104611380A (en) | Low-carbon and environmental-protection sugaring method based on cane sugar alcohol co-production | |
| CN102276378B (en) | Treatment method of fermentation broth | |
| CN103789355B (en) | A kind of method using cellulose containing raw material to prepare ethanol | |
| CN102174590B (en) | Continuous solid state fermentation and product gas stripping coupled separation method for corn | |
| CN110564779A (en) | Method for co-producing biogas by fermenting ethanol with bagasse-molasses mixed raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |