CN103343147B - Method for preparing dibutyl succinate from cassava raw materials - Google Patents
Method for preparing dibutyl succinate from cassava raw materials Download PDFInfo
- Publication number
- CN103343147B CN103343147B CN201310328618.6A CN201310328618A CN103343147B CN 103343147 B CN103343147 B CN 103343147B CN 201310328618 A CN201310328618 A CN 201310328618A CN 103343147 B CN103343147 B CN 103343147B
- Authority
- CN
- China
- Prior art keywords
- succinic acid
- cassava
- liquid
- dibutyl succinate
- temperature
- 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.)
- Active
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 succinic acid preparing technical field, be specifically related to a kind of method being prepared dibutyl succinate by cassava materials.
Background technology
Succinic acid is a kind of very important industrial chemicals, mainly for the preparation of five heterogeneous ring compounds such as succinyl oxides.Also for the preparation of Synolac (Synolac produced by succinic acid has good flexibility, elasticity and water resisting property), paint, dyestuff (diphenyl of succinic acid is the intermediate of dyestuff, generates anthraquinone dye after reacting with aminoanthraquinone), (succinic acid also can do the seasoning of acid condiment for wine, feed, candy etc. to food-flavoring comps.), photographic material etc.In medicine industry available its produce Anticonvulsants, loose phlegm agent, diuretic(s) and the haemostatic medicament such as sulfa drug, vitamin A, vitamins B.As chemical reagent, as alkalimetry standard reagent, buffer reagent, gas-chromatography comparative sample.Also can be used as the raw material of lubricant and tensio-active agent.
The production of current succinic acid is mainly the petrochemical complex route of raw material based on cis-butenedioic anhydride.Oil price fluctuates very large in recent years, and this seriously constrains sustainability and the price steadiness of succinic acid production.On the other hand, chemical synthesis complex process and often need High Temperature High Pressure, this considerably increases the energy and material consumption needed for production; Chemosynthesis simultaneously also can cause serious environmental pollution.
Also occurred that some utilize fermentable to prepare the method for succinic acid, but the raw material used mostly is food crop, cost is high, and 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 is to provide a kind of method being prepared dibutyl succinate by cassava materials, and its cost is low, and productive rate is high, thus eliminates defect in above-mentioned background technology.
For solving the problems of the technologies described above, technical scheme of the present invention is:
Prepared a method for dibutyl succinate by cassava materials, comprise the steps:
The pulverizing of A, cassava block
Choose high-quality cassava block, pulverize with sieve aperture Φ 1.5mm pulverizer, put in a kettle.;
The liquefaction of B, cassava
Add water in reactor, the weight ratio of water and cassava block is 2:1 ~ 3:1, and open and stir, rotating speed 100 ~ 150r/min, power-on is heated to 80 ~ 100 DEG C;
In reactor, add the amylase that amylase activity is 10000U/ml, the weight ratio of amylase and cassava block is 1:200 ~ 1:150, keeps 80 ~ 100 DEG C of constant temperature 0.5 ~ 1.5h;
The saccharification of C, cassava
A, off-response kettle heater, open temperature lowering water, cassava liquefier is down to 55 ~ 65 DEG C, adds the saccharifying enzyme that saccharifying enzymic activity is 10000U/ml, the weight ratio of saccharifying enzyme and cassava block is 1:40 ~ 1:60, opens reactor well heater and keeps 55 ~ 65 DEG C of constant temperature 1 ~ 3h;
B, by cassava saccharified liquid whizzer solid-liquid separation, then use 100 ~ 130 order filter-cloth filterings;
C, the glucose quality percentage composition measured in filtrate, be diluted with water to 18wt% glucose solution;
The sterilizing of D, fermentor tank and feed supplement tank
Fermentor tank and feed supplement tank are put into Autoclave and carries out 120 ~ 140 DEG C of constant temperature sterilizing 30 ~ 60min;
The preparation of E, fermention medium
| Fermention medium title | Content (g/3L) |
| 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 |
| Sodium carbonate | 2.19 |
The sterilizing of F, fermention medium
Fermentation tank culture medium is put into Autoclave and carry out 120 ~ 140 DEG C of constant temperature sterilizing 30 ~ 60min;
The inoculation fermentation of G, substratum
Open automatic temperature control system, the substratum after sterilizing is down to 37 DEG C and keeps temperature constant state;
Fermentor tank rotating speed is adjusted to 180 ~ 230r/min;
With feed supplement liquid, medium pH is adjusted to 5.6 ~ 6.6;
Inoculation Recombinant organism 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 controls between 6.0 ~ 6.2, anaerobically fermenting 72 ~ 0h;
In fermented liquid, institute's succinic acid-producing exists with the form of succinic acid sodium salt;
The filtration of H, fermented liquid and decolouring
Fermented liquid is warming up to 80 ~ 90 DEG C, maintains 30 ~ 60min sterilization;
By ceramic membrane ultrafitration system, fermented liquid is carried out membrane filtration;
Fermented liquid activated carbon decolorizing post after ultrafiltration is decoloured;
The ion-exchange of I, decolouring fermented liquid
Fermented liquid after decolouring enters cationic resin column and carries out ion-exchange, and the Soduxin in fermented liquid is changed into succinic acid;
The evaporation concentration of J, succinic acid solution
200g/l is concentrated into, solution temperature 40 ~ 50 DEG C by entering vacuum evaporation system from the succinic acid solution after friendship;
The crystallization of K, succinic acid concentrated solution
Succinic acid concentrated solution is cooled to 20 DEG C, succinic acid crystallization;
Mother liquor after primary crystallization concentrates again, carries out secondary crystal precipitation;
Mother liquor after secondary crystal concentrates again, carries out three crystallizations;
The drying of L, succinic acid xln
The succinic acid crystal of crystallization is carried out vacuum-drying, obtains qualified succinic acid solid;
M, the succinic acid solid of preparation and butanols are joined in reactor by mole when esterifying catalyst of 1:2 ~ 6;
N, at temperature of reaction is 100 ~ 150 DEG C, make the succinic acid in reactor and butanols generation esterification, the reaction times is 3 ~ 9h, generates succinic acid butyl ester and water;
After in O, reactor, reaction terminates, in still, product is sent in rectifying tower, and remove the moisture in product, the product at the bottom of tower is succinate, comprises dibutyl succinate and succinic acid mono—n—butylester;
The bottom product of P, rectifying tower sends into catalytic rectifying tower rectifying section, catalytic rectifying tower processing condition are: pressure 0.1 ~ 0.5MPa, bottom temperature 120 ~ 180 DEG C, tower top temperature 90 ~ 120 DEG C, catalytic rectifying tower stripping section presses rectifying section charging succinate mol ratio 1:1 ~ 5 input butanols simultaneously;
Q, the discharging of catalytic distillation column overhead are butanols and water, at the bottom of tower, take out described dibutyl succinate.
Improve as one, fermented bacterium is gene engineering strain producing succinic acid escherichia coli, and preserving number is: CGMCC No.4512.
Improve as one, in described ceramic membrane ultrafitration system, ceramic membrane aperture is 50nm.
Improve as one, in described cationic resin column, adopt 732 type Zeo-karbs.
Improve as one, described catalytic rectifying tower is a kind of chemical industry equipment esterification and rectifying are coupled.That is, the bottom of this catalytic rectifying tower is catalytic esterification tower body, and top is coupled with rectifying tower.
In the present invention, in fermented liquid institute's succinic acid-producing be with the form of succinic acid sodium salt exist, molecular weight be 118 succinic acid concentration reach 110g/l, glucose acid invert ratio 0.95 ~ 1.05g/g.
In the present invention, fermention medium is minimal medium.
In the present invention, feed supplement liquid is the mixing solutions of sodium hydroxide and sodium carbonate, and its mass ratio is 0.7:1.
The finished product succinic acid purity utilizing the present invention to produce is greater than 99.5%, and yield is greater than 92%.
In the present invention, the dibutyl succinate taken out at the bottom of described catalytic rectifying tower tower, impurity is considerably less, mass percentage >=99.5% of dibutyl succinate, succinic acid mono—n—butylester≤0.1%.
Owing to have employed technique scheme, the invention has the beneficial effects as follows:
Present invention employs cassava as raw material, cassava is different from the traditional food crop such as corn, wheat, cheap, belong to renewable resources, and starch content is very high in cassava, the present invention adopts non-grain raw material to utilize biological fermentation process to prepare succinic acid, decreases environmental pollution, more meets national existing policy.
In the present invention, first by the pulverizing of cassava block, liquefaction, saccharification, utilize sieve aperture Φ 1.5mm pulverizer to pulverize during pulverizing, during liquefaction, the weight ratio of water and cassava block is 2:1 ~ 3:1, open and stir, rotating speed 100 ~ 150r/min, power-on is heated to 80 ~ 100 DEG C, adds the amylase that amylase activity is 10000U/ml in reactor, the weight ratio of amylase and cassava block is 1:200 ~ 1:150, keeps 80 ~ 100 DEG C of constant temperature 0.5 ~ 1.5h; During saccharification, cassava liquefier is down to 55 ~ 65 DEG C, adds the saccharifying enzyme that saccharifying enzymic activity is 10000U/ml, the weight ratio of saccharifying enzyme and cassava block is 1:40 ~ 1:60, keep 55 ~ 65 DEG C of constant temperature 1 ~ 3h, use whizzer solid-liquid separation, then use 100 ~ 130 order filter-cloth filterings.More than that contriver is after prolonged and repeated experiment, the processing step formulated for this specific non-grain raw material of cassava, in fact, when utilizing above-mentioned steps to process cassava, can the abundant saccharification by the starch in cassava, Starch Conversion rate is more than 98%.Contriver also attempted other traditional methods, such as, change some step in above-mentioned technique or processing parameter, but effect is all undesirable, and in an experiment, when not adopting above-mentioned technique, in cassava, Starch Conversion rate is up to 90%.Visible, during process to cassava, adopt above-mentioned steps, reach very significant effect.
Present invention employs special bacterial classification, be colon bacillus (Escherichia coli) XZT124, preserving number is CGMCC No.4512, and according to the feature of cassava, in conjunction with the characteristic of bacterial classification, after a large amount of experiment repeatedly, have selected the operational path that meets suitability for industrialized production more.In the fermention medium in early stage, containing cassava Glucose Liquid, primary ammonium phosphate, Secondary ammonium phosphate, magnesium sulfate heptahydrate, Repone K, trace metal salts, bacterial classification not only can be made just can to adapt to cassava materials environment early stage, and enough inorganic salt and other material can be provided; In addition, devise the pH that feed supplement liquid is used for adjusting substratum, when formally fermenting, inoculation Recombinant organism 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.In the fermented liquid obtained, institute's succinic acid-producing exists with the form of succinic acid sodium salt, molecular weight be 118 succinic acid concentration reach 110g/l, repeatedly sampling and measuring through contriver calculates, and finds that glucose acid invert ratio 0.95 ~ 1.05g/g(theoretical upper values is 1.12g/g).That is, adopt specific bacterial classification in the present invention, specific technique, cassava materials is fermented, serves the effect of highly significant.
The present invention also adopts specific technique to carry out aftertreatment to fermented liquid, to obtain qualified succinic acid crystal, first sterilization, by ceramic membrane ultrafitration system, fermented liquid is carried out membrane filtration, the fermented liquid activated carbon decolorizing post after ultrafiltration is decoloured, then enters cationic resin column and carry out ion-exchange, vacuum evaporation system is adopted to be concentrated into 200g/l, solution temperature 40 ~ 50 DEG C, finally adopts three crystallizations, obtains qualified succinic acid solid after vacuum-drying.In aftertreatment, do not introduce other impurity, ensure that the purity of succinic acid.
The present invention is directed to the succinic acid utilizing cassava to produce, devise rational step, adopt first pre-esterification, again rectifying, then enter the method that catalytic rectifying tower carries out degree of depth esterification, the dibutyl succinate impurity of final production is considerably less, mass percentage >=99.5% of dibutyl succinate, succinic acid mono—n—butylester≤0.1%.
In a word, most important significance of the present invention is, have selected rational processing step, and non-grain crop-cassava is carried out pre-treatment, then select specific bacterial classification, cassava materials liquid is fermented, obtained succinic acid, and in preparation process, glucose acid invert ratio is very high, more complete to the utilization of cassava.
Be compared to the food crop that corn, wheat etc. are traditional, cost of the present invention is lower.When glucose acid invert ratio is identical, the present invention produces succinic acid cost per ton at 6000 ~ 7000 yuan, and utilizes Maize Production succinic acid cost per ton at about 10000 yuan, high by about 40%.
Embodiment
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
Embodiment 1
Prepared a method for dibutyl succinate by cassava materials, adopt following steps:
The pulverizing of A, cassava block
Choose high-quality cassava block, pulverize with sieve aperture Φ 1.5mm pulverizer, put in a kettle.;
The liquefaction of B, cassava
Add water in reactor, the weight ratio of water and cassava block is 2:1, and open and stir, rotating speed 100r/min, power-on is heated to 80 DEG C;
In reactor, add the amylase that amylase activity is 10000U/ml, the weight ratio of amylase and cassava block is 1:200, keeps 80 DEG C of constant temperature 0.5h;
The saccharification of C, cassava
A, off-response kettle heater, open temperature lowering water, cassava liquefier is down to 55 DEG C, adds the saccharifying enzyme that saccharifying enzymic activity is 10000U/ml, the weight ratio of saccharifying enzyme and cassava block is 1:40, opens reactor well heater and keeps 55 DEG C of constant temperature 1h;
B, by cassava saccharified liquid whizzer solid-liquid separation, then use 100 order filter-cloth filterings;
C, the glucose quality percentage composition measured in filtrate, be diluted with water to 18wt% glucose solution;
The sterilizing of D, fermentor tank and feed supplement tank
Fermentor tank and feed supplement tank are put into Autoclave and carries out 120 ~ 140 DEG C of constant temperature sterilizing 30 ~ 60min;
The preparation of E, fermention medium
| Fermention medium title | Content (g/3L) |
| 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 |
| Sodium carbonate | 2.19 |
The sterilizing of F, fermention medium
Fermentation tank culture medium is put into Autoclave and carry out 120 DEG C of constant temperature sterilizing 30min;
The inoculation fermentation of G, substratum
Open automatic temperature control system, the substratum after sterilizing is down to 37 DEG C and keeps temperature constant state;
Fermentor tank rotating speed is adjusted to 180r/min;
With feed supplement liquid, medium pH is adjusted to 5.6;
Employing fermented bacterium is gene engineering strain producing succinic acid escherichia coli, and preserving number is: CGMCC No.4512; Inoculation Recombinant organism 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;
In fermented liquid, institute's succinic acid-producing exists with the form of succinic acid sodium salt; Molecular weight be 118 succinic acid concentration reach 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 DEG C, maintains 30min sterilization;
By ceramic membrane ultrafitration system, fermented liquid is carried out membrane filtration, in described ceramic membrane ultrafitration system, ceramic membrane aperture is 50nm;
Fermented liquid activated carbon decolorizing post after ultrafiltration is decoloured;
The ion-exchange of I, decolouring fermented liquid
Fermented liquid after decolouring enters cationic resin column and carries out ion-exchange, and the Soduxin in fermented liquid is changed into succinic acid, adopts 732 type Zeo-karbs in described cationic resin column;
The evaporation concentration of J, succinic acid solution
200g/l is concentrated into, solution temperature 40 ~ 50 DEG C by entering vacuum evaporation system from the succinic acid solution after friendship;
The crystallization of K, succinic acid concentrated solution
Succinic acid concentrated solution is cooled to 20 DEG C, succinic acid crystallization;
Mother liquor after primary crystallization concentrates again, carries out secondary crystal precipitation;
Mother liquor after secondary crystal concentrates again, carries out three crystallizations;
The drying of L, succinic acid xln
The succinic acid crystal of crystallization is carried out vacuum-drying, obtains qualified succinic acid solid;
M, the succinic acid solid of preparation and butanols are joined in reactor by mole when esterifying catalyst of 1:2;
N, at temperature of reaction is 100 DEG C, make the succinic acid in reactor and butanols generation esterification, the reaction times is 3h, generates succinic acid butyl ester and water;
After in O, reactor, reaction terminates, in still, product is sent in rectifying tower, and remove the moisture in product, the product at the bottom of tower is succinate, comprises dibutyl succinate and succinic acid mono—n—butylester;
The bottom product of P, rectifying tower sends into catalytic rectifying tower rectifying section, and catalytic rectifying tower processing condition are: pressure 0.1MPa, bottom temperature 120 DEG C, tower top temperature 90 DEG C, and catalytic rectifying tower stripping section is pressed rectifying section charging succinate mol ratio 1:5 and inputted butanols simultaneously;
Q, the discharging of catalytic distillation column overhead are butanols and water, at the bottom of tower, take out described dibutyl succinate.
Contriver, in strict accordance with above processing parameter, utilizes the cassava materials of 1.6 tons, prepares the succinic acid solid of 1100 kilograms, and output ratio is 1:0.69; And then prepare 2057kg dibutyl succinate, the purity obtaining dibutyl succinate is after testing 99.5%.
Embodiment 2
Prepared a method for dibutyl succinate by cassava materials, comprise the steps:
The pulverizing of A, cassava block
Choose high-quality cassava block, pulverize with sieve aperture Φ 1.5mm pulverizer, put in a kettle.;
The liquefaction of B, cassava
Add water in reactor, the weight ratio of water and cassava block is 2.5:1, and open and stir, rotating speed 120r/min, power-on is heated to 90 DEG C;
In reactor, add the amylase that amylase activity is 10000U/ml, the weight ratio of amylase and cassava block is 1:170, keeps 90 DEG C of constant temperature 1.0h;
The saccharification of C, cassava
A, off-response kettle heater, open temperature lowering water, cassava liquefier is down to 60 DEG C, adds the saccharifying enzyme that saccharifying enzymic activity is 10000U/ml, the weight ratio of saccharifying enzyme and cassava block is 1:50, opens reactor well heater and keeps 60 DEG C of constant temperature 1 ~ 3h;
B, by cassava saccharified liquid whizzer solid-liquid separation, then use 120 order filter-cloth filterings;
C, the glucose quality percentage composition measured in filtrate, be diluted with water to 18wt% glucose solution;
The sterilizing of D, fermentor tank and feed supplement tank
Fermentor tank and feed supplement tank are put into Autoclave and carries out 130 DEG C of constant temperature sterilizing 45min;
The preparation of E, fermention medium
| Fermention medium title | Content (g/3L) |
| 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 |
| Sodium carbonate | 2.19 |
The sterilizing of F, fermention medium
Fermentation tank culture medium is put into Autoclave and carry out 130 DEG C of constant temperature sterilizing 45min;
The inoculation fermentation of G, substratum
Open automatic temperature control system, the substratum after sterilizing is down to 37 DEG C and keeps temperature constant state;
Fermentor tank rotating speed is adjusted to 200r/min;
With feed supplement liquid, medium pH is adjusted to 6.0;
Employing fermented bacterium is gene engineering strain producing succinic acid escherichia coli, and preserving number is: CGMCCNo.4512; Inoculation Recombinant organism 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;
In fermented liquid, institute's succinic acid-producing exists with the form of succinic acid sodium salt; Molecular weight be 118 succinic acid concentration reach 110g/l, glucose acid invert ratio 1.05g/g.
The filtration of H, fermented liquid and decolouring
Fermented liquid is warming up to 85 DEG C, maintains 45min sterilization;
By ceramic membrane ultrafitration system, fermented liquid is carried out membrane filtration, in described ceramic membrane ultrafitration system, ceramic membrane aperture is 50nm;
Fermented liquid activated carbon decolorizing post after ultrafiltration is decoloured;
The ion-exchange of I, decolouring fermented liquid
Fermented liquid after decolouring enters cationic resin column and carries out ion-exchange, and the Soduxin in fermented liquid is changed into succinic acid, adopts 732 type Zeo-karbs in described cationic resin column;
The evaporation concentration of J, succinic acid solution
200g/l is concentrated into, solution temperature 45 DEG C by entering vacuum evaporation system from the succinic acid solution after friendship;
The crystallization of K, succinic acid concentrated solution
Succinic acid concentrated solution is cooled to 20 DEG C, succinic acid crystallization;
Mother liquor after primary crystallization concentrates again, carries out secondary crystal precipitation;
Mother liquor after secondary crystal concentrates again, carries out three crystallizations;
The drying of L, succinic acid xln
The succinic acid crystal of crystallization is carried out vacuum-drying, obtains qualified succinic acid solid;
M, the succinic acid solid of preparation and butanols are joined in reactor by mole when esterifying catalyst of 1:6;
N, at temperature of reaction is 150 DEG C, make the succinic acid in reactor and butanols generation esterification, the reaction times is 9h, generates succinic acid butyl ester and water;
After in O, reactor, reaction terminates, in still, product is sent in rectifying tower, and remove the moisture in product, the product at the bottom of tower is succinate, comprises dibutyl succinate and succinic acid mono—n—butylester;
The bottom product of P, rectifying tower sends into catalytic rectifying tower rectifying section, catalytic rectifying tower processing condition are: pressure 0.3MPa, bottom temperature 150 DEG C, tower top temperature 105 DEG C, catalytic rectifying tower stripping section is pressed rectifying section charging succinate mol ratio 1:3 and is inputted butanols simultaneously;
Q, the discharging of catalytic distillation column overhead are butanols and water, at the bottom of tower, take out described dibutyl succinate.
Contriver, in strict accordance with above processing parameter, utilizes the cassava materials of 1.6 tons, prepares the succinic acid solid of 1200 kilograms, and output ratio is 1:0.75; And then prepare 2295kg dibutyl succinate, detect and find: finished product succinic acid purity is 99.8%; The purity of dibutyl succinate is 99.8%.
Embodiment 3
Prepared a method for dibutyl succinate by cassava materials, comprise the steps:
The pulverizing of A, cassava block
Choose high-quality cassava block, pulverize with sieve aperture Φ 1.5mm pulverizer, put in a kettle.;
The liquefaction of B, cassava
Add water in reactor, the weight ratio of water and cassava block is 3:1, and open and stir, rotating speed 150r/min, power-on is heated to 100 DEG C;
In reactor, add the amylase that amylase activity is 10000U/ml, the weight ratio of amylase and cassava block is 1:150, keeps 100 DEG C of constant temperature 1.5h;
The saccharification of C, cassava
A, off-response kettle heater, open temperature lowering water, cassava liquefier is down to 65 DEG C, adds the saccharifying enzyme that saccharifying enzymic activity is 10000U/ml, the weight ratio of saccharifying enzyme and cassava block is 1:60, opens reactor well heater and keeps 65 DEG C of constant temperature 3h;
B, by cassava saccharified liquid whizzer solid-liquid separation, then use 130 order filter-cloth filterings;
C, the glucose quality percentage composition measured in filtrate, be diluted with water to 18wt% glucose solution;
The sterilizing of D, fermentor tank and feed supplement tank
Fermentor tank and feed supplement tank are put into Autoclave and carries out 140 DEG C of constant temperature sterilizing 60min;
The preparation of E, fermention medium
| Fermention medium title | Content (g/3L) |
| 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 |
| Sodium carbonate | 2.19 |
The sterilizing of F, fermention medium
Fermentation tank culture medium is put into Autoclave and carry out 140 DEG C of constant temperature sterilizing 60min;
The inoculation fermentation of G, substratum
Open automatic temperature control system, the substratum after sterilizing is down to 37 DEG C and keeps temperature constant state;
Fermentor tank rotating speed is adjusted to 230r/min;
With feed supplement liquid, medium pH is adjusted to 6.6;
Inoculation Recombinant organism 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;
In fermented liquid, institute's succinic acid-producing exists with the form of succinic acid sodium salt; Molecular weight be 118 succinic acid concentration reach 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 DEG C, maintains 60min sterilization;
By ceramic membrane ultrafitration system, fermented liquid is carried out membrane filtration, in described ceramic membrane ultrafitration system, ceramic membrane aperture is 50nm;
Fermented liquid activated carbon decolorizing post after ultrafiltration is decoloured;
The ion-exchange of I, decolouring fermented liquid
Fermented liquid after decolouring enters cationic resin column and carries out ion-exchange, and the Soduxin in fermented liquid is changed into succinic acid, adopts 732 type Zeo-karbs in described cationic resin column;
The evaporation concentration of J, succinic acid solution
200g/l is concentrated into, solution temperature 50 DEG C by entering vacuum evaporation system from the succinic acid solution after friendship;
The crystallization of K, succinic acid concentrated solution
Succinic acid concentrated solution is cooled to 20 DEG C, succinic acid crystallization;
Mother liquor after primary crystallization concentrates again, carries out secondary crystal precipitation;
Mother liquor after secondary crystal concentrates again, carries out three crystallizations;
The drying of L, succinic acid xln
The succinic acid crystal of crystallization is carried out vacuum-drying, obtains qualified succinic acid solid;
M, the succinic acid solid of preparation and butanols are joined in reactor by mole when esterifying catalyst of 1:4;
N, at temperature of reaction is 120 DEG C, make the succinic acid in reactor and butanols generation esterification, the reaction times is 7h, generates succinic acid butyl ester and water;
After in O, reactor, reaction terminates, in still, product is sent in rectifying tower, and remove the moisture in product, the product at the bottom of tower is succinate, comprises dibutyl succinate and succinic acid mono—n—butylester;
The bottom product of P, rectifying tower sends into catalytic rectifying tower rectifying section, catalytic rectifying tower processing condition are: pressure 0.5MPa, bottom temperature 180 DEG C, tower top temperature 120 DEG C, catalytic rectifying tower stripping section is pressed rectifying section charging succinate mol ratio 1:3 and is inputted butanols simultaneously;
Q, the discharging of catalytic distillation column overhead are butanols and water, at the bottom of tower, take out described dibutyl succinate.
Contriver, in strict accordance with above processing parameter, utilizes the cassava materials of 1.6 tons, and prepare the succinic acid solid of 1136 kilograms, output ratio is 1:0.7, and then prepares 1987kg dibutyl succinate, detects and finds: finished product succinic acid purity is 99.5%; The purity of dibutyl succinate is 99.6%.
As can be seen from above-described embodiment also, when step in strict accordance with embodiment 2, the output ratio of succinic acid solid of the present invention is the highest, apparently higher than embodiment 1 and embodiment 3.
Comparative example 1
Due to the detailed record not utilizing biological fermentation process to produce succinic acid at present, therefore, comparative example 1 adopts the step identical with embodiment 2.
Difference is, this comparative example utilizes food crop corn as raw material, and bacterial classification adopts traditional natural succinic acid-producing bacterium.
Result is as follows:
Raw material is 100kg corn, and the succinic acid solid masses of output is 63kg, and output ratio is 1:0.63; The purity of succinic acid solid is 99.5%.
Visible, when utilizing corn as raw material, for using cassava as raw material, output ratio is very low.And cost is very high.Contriver contrasts other food crop such as wheats simultaneously, and result is consistent.
Comparative example 2
Take corn as raw material, step is in strict accordance with the step of embodiment 2, and bacterial classification adopts bacterial classification provided by the invention.
Result is as follows:
Raw material is 100kg corn, and the succinic acid solid masses of output is 64kg, and output ratio is 1:0.64; The purity of succinic acid solid is 99.5%.
Visible, for using cassava as raw material, even if when adopting identical bacterial classification, when utilizing corn as raw material, the output ratio of succinic acid is still very low, and cost is very high.Contriver contrasts other food crop such as wheats simultaneously, and result is consistent.
Comparative example 3
Take cassava as raw material, 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 in embodiment 2, its glucose solution is fermented again after generating glucose solution.
Result is as follows:
Raw material is 100kg cassava, and the succinic acid solid masses of output is 64kg, and output ratio is 1:0.64; The purity of succinic acid solid is 99.5%.
Visible, when not adopting cassava pre-treating technology provided by the invention, the output ratio also corresponding minimizing of succinic acid.The yield effect of pre-treatment step of the present invention to later stage succinic acid solid is very large.
Comparative example 4
Take cassava as raw material, the step provided in strict accordance with embodiment 2 is carried out, and difference have employed traditional natural succinic acid-producing bacterium as bacterial classification, and fermentation condition is chosen as the optimal conditions of this bacterial classification.
Result is as follows:
Raw material is 100kg cassava, and the succinic acid solid masses of output is 59kg, and output ratio is 1:0.59; The purity of succinic acid solid is 99.5%.
Visible, when not adopting cassava pre-treating technology provided by the invention, the output ratio of succinic acid greatly reduces.When adopting cassava to be raw material, adopt specific bacterial classification very large to the yield effect of succinic acid solid.
Comparative example 5
Take cassava as raw material, step is in strict accordance with the step of embodiment 2, and bacterial classification adopts bacterial classification provided by the invention.Difference is, after obtaining succinic acid solid, adopts traditional dibutyl succinate preparation method, by succinic acid solid directly and butanols react, both mol ratios are 1:3 ~ 6.
Result is as follows:
Raw material is 100kg cassava, and the succinic acid solid masses of output is 74kg, and output ratio is 1:0.74; And obtained dibutyl succinate quality is only 103kg, and the purity of dibutyl succinate is only 85.3%, and wherein the massfraction of succinic acid mono—n—butylester is up to 11.3%, and all the other are other impurity.
Visible, 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 cannot be protected.
The present invention is not limited to above-mentioned embodiment, and all are based on technical conceive of the present invention, and done structural improvement, all falls among protection scope of the present invention.
Claims (3)
1. prepared a method for dibutyl succinate by cassava materials, it is characterized in that: comprise the steps:
The pulverizing of A, cassava block
Choose high-quality cassava block, pulverize with sieve aperture Φ 1.5mm pulverizer, put in a kettle.;
The liquefaction of B, cassava
Add water in reactor, the weight ratio of water and cassava block is 2:1 ~ 3:1, and open and stir, rotating speed 100 ~ 150r/min, is heated to 80 ~ 100 DEG C;
In reactor, add the amylase that amylase activity is 10000U/ml, the weight ratio of amylase and cassava block is 1:200 ~ 1:150, keeps 80 ~ 100 DEG C of constant temperature 0.5 ~ 1.5h;
The saccharification of C, cassava
A, off-response kettle heater, open temperature lowering water, cassava liquefier is down to 55 ~ 65 DEG C, adds the saccharifying enzyme that saccharifying enzymic activity is 10000U/ml, the weight ratio of saccharifying enzyme and cassava block is 1:40 ~ 1:60, opens reactor well heater and keeps 55 ~ 65 DEG C of constant temperature 1 ~ 3h;
B, by cassava saccharified liquid whizzer solid-liquid separation, then use 100 ~ 130 order filter-cloth filterings;
C, the glucose quality percentage composition measured in filtrate, be diluted with water to 18wt% glucose solution;
The sterilizing of D, fermentor tank and feed supplement tank
Fermentor tank and feed supplement tank are put into Autoclave and carries out 120 ~ 140 DEG C of constant temperature sterilizing 30 ~ 60min;
The preparation of E, fermention medium
The sterilizing of F, fermention medium
Fermentation tank culture medium is put into Autoclave and carry out 120 ~ 140 DEG C of constant temperature sterilizing 30 ~ 60min;
The inoculation fermentation of G, substratum
Open automatic temperature control system, the substratum after sterilizing is down to 37 DEG C and keeps temperature constant state;
Fermentor tank rotating speed is adjusted to 180 ~ 230r/min;
With feed supplement liquid, medium pH is adjusted to 5.6 ~ 6.6;
Inoculation Recombinant organism strain seed liquor, the volume ratio of seed liquor and fermention medium is 1:90 ~ 1:110, and described fermented bacterium is gene engineering strain producing succinic acid escherichia coli, and preserving number is: CGMCC No.4512;
Open peristaltic pump, auto-feeding feed supplement liquid, pH controls 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 DEG C, maintains 30 ~ 60min sterilization;
By ceramic membrane ultrafitration system, fermented liquid is carried out membrane filtration;
Fermented liquid activated carbon decolorizing post after ultrafiltration is decoloured;
The ion-exchange of I, decolouring fermented liquid
Fermented liquid after decolouring enters cationic resin column and carries out ion-exchange, and the Soduxin in fermented liquid is changed into succinic acid;
The evaporation concentration of J, succinic acid solution
200g/l is concentrated into, solution temperature 40 ~ 50 DEG C by entering vacuum evaporation system from the succinic acid solution after friendship;
The crystallization of K, succinic acid concentrated solution
Succinic acid concentrated solution is cooled to 20 DEG C, succinic acid crystallization;
Mother liquor after primary crystallization concentrates again, carries out secondary crystal precipitation;
Mother liquor after secondary crystal concentrates again, carries out three crystallizations;
The drying of L, succinic acid xln
The succinic acid crystal of crystallization is carried out vacuum-drying, obtains qualified succinic acid solid;
M, the succinic acid solid of preparation and butanols are joined in reactor by mole when esterifying catalyst of 1:2 ~ 6;
N, at temperature of reaction is 100 ~ 150 DEG C, make the succinic acid in reactor and butanols generation esterification, the reaction times is 3 ~ 9h, generates succinic acid butyl ester and water;
After in O, reactor, reaction terminates, in still, product is sent in rectifying tower, and remove the moisture in product, the product at the bottom of tower is succinate, comprises dibutyl succinate and succinic acid mono—n—butylester;
The bottom product of P, rectifying tower sends into catalytic rectifying tower rectifying section, catalytic rectifying tower processing condition are: pressure 0.1 ~ 0.5MPa, bottom temperature 120 ~ 180 DEG C, tower top temperature 90 ~ 120 DEG C, catalytic rectifying tower stripping section presses rectifying section charging succinate mol ratio 1:1 ~ 5 input butanols simultaneously, and described catalytic rectifying tower is a kind of equipment esterification and rectifying are coupled;
Q, the discharging of catalytic distillation column overhead are butanols and water, at the bottom of tower, take out described dibutyl succinate.
2. a kind of method being prepared dibutyl succinate by cassava materials as claimed in claim 1, is characterized in that: in described ceramic membrane ultrafitration system, ceramic membrane aperture is 50nm.
3. a kind of method being prepared dibutyl succinate by cassava materials as claimed in claim 1, is characterized in that: adopt 732 type Zeo-karbs in described cationic resin column.
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 CN103343147A (en) | 2013-10-09 |
| CN103343147B true 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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108101744B (en) * | 2017-12-14 | 2018-12-11 | 四川安益生物科技有限公司 | Inositol extraction method |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033024C (en) * | 1992-01-15 | 1996-10-16 | 黄玉龙 | Process for extraction of dicarboxylic acid and its esters from waste liquid after production of hexandioic acid |
| TW200944499A (en) * | 2008-04-17 | 2009-11-01 | Univ Nat Taiwan | Method and apparatus for producing diester |
| CN101348429B (en) * | 2008-09-05 | 2011-03-16 | 江南大学 | Method for extracting amber acid in fermentation liquor by cationic resin exchange |
| CN102174455B (en) * | 2011-01-28 | 2012-11-21 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN103343147A (en) | 2013-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103361385B (en) | Technology for preparation of succinic acid finished product by bioconversion of cassava raw material | |
| CN101805767B (en) | High-purity isomaltose hypgather and alcohol co-production preparation method | |
| CN102061316A (en) | Preparation method of long carbon chain dibasic acid | |
| CN100540671C (en) | The mixed raw-material fermenting process of Alcohol Production | |
| CN104611381A (en) | Method for producing ethanol by continuous enzymolysis and fermentation of lignocellulose | |
| CN101608192B (en) | Method for producing succinic acid employing corn cob | |
| CN104630311A (en) | Method for synchronously producing straw nano-cellulose and bacterial cellulose by using sweet sorghum | |
| CN103343147B (en) | Method for preparing dibutyl succinate from cassava raw materials | |
| WO2016173262A1 (en) | Method for producing cellulosic ethanol by fermenting agricultural and forest biomass waste thick mash | |
| Jampatesh et al. | Evaluation of inhibitory effect and feasible utilization of dilute acid-pretreated rice straws on succinate production by metabolically engineered Escherichia coli AS1600a | |
| CN107058403A (en) | A kind of distiller's grains liquor is used for the method that full amylofermentation prepares ethanol | |
| CN104830918A (en) | Novel production method of sodium gluconate | |
| CN101878308B (en) | A process for the preparation of ethanol from starch | |
| CN103789354A (en) | Method for preparing ethanol from cellulose-containing raw material | |
| CN104651416A (en) | Method for synchronously producing biological butanol and nano cellulose from sweet sorghum | |
| CN102796787B (en) | Preparation method of corn starch sugar | |
| CN105586368B (en) | A kind of method of the processing method and fermentation production of citric acid of sorghum seed | |
| CN116426577A (en) | Calcium hydroxide as neutralizer combined with CO 2 Method for producing succinic acid by pulse feedback feed supplement fermentation | |
| CN101696429A (en) | Method for producing butanol by hydrolyzing and fermenting waste crops rich in hemicellulose | |
| CN102051386A (en) | Method for producing organic acid at high production rate through fermentation of intermittent backflow cells | |
| CN110564780B (en) | Method for co-production of biogas by fermenting ethanol with bagasse-molasses-yam residue mixed raw material | |
| CN104611380A (en) | Low-carbon and environmental-protection sugaring method based on cane sugar alcohol co-production | |
| CN105624219A (en) | Method for producing citric acid by fermenting wheat starch milk | |
| CN110564779A (en) | Method for co-producing biogas by fermenting ethanol with bagasse-molasses mixed raw material | |
| CN112175999B (en) | Fermentation treatment method of corn soaking liquid, liquid phase product obtained by using fermentation treatment method and application of liquid phase product |
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 |