CN104450806A - Method for preparing sodium gluconate with enzymatic method - Google Patents
Method for preparing sodium gluconate with enzymatic method Download PDFInfo
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Abstract
The invention discloses a method for preparing sodium gluconate with an enzymatic method and belongs to the technical field of biochemistry. The method comprises steps as follows: glucose has an oxidation reaction with oxygen and water under the catalytic action of a glucose oxidase to produce gluconic acid and hydrogen peroxide, the hydrogen peroxide is decomposed into water and oxygen under the action of a catalase, and the gluconic acid has a neutralization reaction with sodium hydroxide to produce the sodium gluconate; the finished product, namely, the sodium gluconate, is obtained through enzyme deactivation, decolorization, concentration, crystallization and drying. The method can be used for producing food-grade and medicine-grade sodium gluconate and has the advantages that the operation is simple, the reaction time is short, the sodium gluconate is high in purity, little waste is produced and the like.
Description
Technical field
The present invention relates to a kind of method that enzyme process prepares Sunmorl N 60S, belong to technological field of biochemistry.
Background technology
Sunmorl N 60S is a kind of organic acid salt of multihydroxyl, is widely used in the industries such as chemical industry, food, medicine, building.The production method of current Sunmorl N 60S mainly contains four kinds of methods such as eletrooxidation method, electrolytic oxidation, heterogeneous catalytic oxidation method and biological fermentation process.Eletrooxidation method take crystalline dextrose as raw material, catalyzer is added after being dissolved in water by crystalline dextrose, under certain temperature of reaction, add people chlorine bleach liquor, drip alkali lye makes equilibrium system move to the generation direction of Sunmorl N 60S simultaneously, after reaction terminates, namely obtain Sunmorl N 60S product by condensing crystal.This technological process is easy to manipulation, but Sunmorl N 60S productive rate is low, can be mixed with sodium chloride as impurity in product, and the application of product is restricted.Electrolytic oxidation is based on electrochemical principle, add a certain amount of glucose solution and suitable ionogen in a cell in advance, control temperature of reaction, then carry out electrolytic reaction to the electric current that electrolyzer people is constant, after electrolysis terminates, namely electrolytic solution condensing crystal is obtained gluconic acid sodium crystal.Electrolytic oxidation production cost is higher, and equipment is complicated, and reaction should not control, and is not suitable for suitability for industrialized production.Heterogeneous catalytic oxidation method is in retort, add the certain density glucose solution of people and catalyzer, appropriate air is passed into again in reaction system, control constant temperature of reaction and pH, after reaction terminates, after filtration, condensing crystal, centrifugal drying obtain gluconic acid sodium crystal.This technique is simple, and quality product is better, but catalyzer cost is higher.Biological fermentation process adds mass propgation base with seed liquor to carry out fermentative production Sunmorl N 60S.Along with the seed selection of excellent species can tolerate higher concentration of substrate.But to add due to a large amount of substratum and by product brings very burden to the Hydrolysis kinetics in later stage, directly have influence on quality and the transformation efficiency of product.
Summary of the invention
The invention provides a kind of method by enzyme Direct Catalytic Oxidation glucose production Sunmorl N 60S, overcome existing production technology shortcoming, the advantages such as have transformation efficiency high, the production time is short, and product purity is high, and technique is simple.
Technical scheme of the present invention be by glucose under the catalysis of glucose oxidase, gluconic acid and hydrogen peroxide is produced with oxygen G&W generation oxidizing reaction, hydrogen peroxide is decomposed into water and oxygen under catalatic effect, and gluconic acid then produces Sunmorl N 60S with sodium hydroxide generation neutralization reaction.Further, finished product Sunmorl N 60S is obtained through the enzyme that goes out, decolouring, concentrated, crystallization, drying.
Described enzymic catalytic reaction equation is:
4C
6H
12O
6+3O
2+2H
2O→4C
6H
12O
7+2H
2O
2
H
2O
2→2H
2O+O
2
C
6H
12O
7+NaOH→C
6H
11O
7Na+H
2O
The present invention mainly comprises the following steps: (1) enzyme reaction: in the glucose solution of massfraction 35-40%, once or in batches add glucose oxidase and catalase, stream adds the sodium hydroxide solution of massfraction 40-50% to maintain pH value of solution 5.0-7.0, holding temperature 38 ± 1 DEG C, pass into pressurized air, air flow is 0.5-1vvm, maintain tank pressure 0.2-0.5MPa, mixing speed is 250-300r/min, reaction times 20-24 hour; Record residual sugar <0.3%, stream hydro-oxidation sodium reaches theoretical reaction requirement amount, and regulates pH to be 6.5-7.5, and after maintaining 20-30min, catalyzed reaction terminates.(2) to go out enzyme and decolouring: react after terminating, add gac and heat, filter and obtain colourless solution.(3) concentrated: will filter the solution obtained, reduction vaporization concentrates, and obtains the solution that Sunmorl N 60S massfraction is greater than 70%.(4) crystallizing and drying: by solution fluidised bed drying.
In one embodiment of the invention, step (1) glucose oxidase addition is 5000-10000U/ml, and catalase addition is 10-20 ten thousand U/ml.
In another embodiment of the invention, step (1) glucose oxidase addition is 6000U/ml, and catalase addition is 100,000 U/ml.
In one embodiment of the invention, the described reaction end of step (1) refers to as residual sugar <0.3% in reaction process, the sodium hydroxide solution that stream adds reaches theoretical addition, regulates pH to be 6.5-7.5 and to maintain for some time no longer to change.In theory, 1 mol Glucose will consume 1 molar sodium hydroxide.
In one embodiment of the invention, step (2) is the powdered active carbon adding 2-5% in reaction solution, and ebuillition of heated 5-20min, then cross and filter protein and pigment.Described filtration can be suction filtration or Plate Filtration.
In one embodiment of the invention, the filtrate through go out enzyme and decolouring at negative 0.07-0.09MPa, is evaporated to gluconic acid na concn at temperature 80 DEG C and reaches more than 70% by step (3).
The Sunmorl N 60S drying crystalline final content >99.4% that the present invention obtains, is greater than 90% with the glucose meter rate of recovery, and reaches first grade and top grade product standard.This invention simplifies production technique, more existing production method compares less investment, and plant factor is high, with short production cycle, and the impurity introduced in reaction process is few, by product is few, and the purification processes in later stage is very simple, can obtain the Sunmorl N 60S that purity is high.
Accompanying drawing explanation
Fig. 1 technological process of production of the present invention
Embodiment
Embodiment 1
20L 40% glucose solution is added in 30L tank, add 150mL (to 6000U/ml) glucose oxidase simultaneously, 75 (to 100,000 U/ml) mL catalase, setting reaction pH is 6.0, and the sodium hydroxide stream with 50% adds adjustment pH, maintain temperature of reaction 38 DEG C, pass into pressurized air, air flow is 0.5vvm, maintains tank pressure 0.2MPa, open and stir, rotating speed is 250-300r/min.React about 24 hours, record residual sugar <0.3%, stream adds 50% sodium hydroxide and reaches 3.56L, and is 7.0 by reaction pH regulator, and maintain half an hour, catalyzed reaction terminates.After reaction terminates, add 600g gac and be heated to the 5min that seethes with excitement, micropore suction filtration obtains colourless solution, the solution obtained by suction filtration, at negative 0.08MPa, is evaporated to and is greater than 70% concentration, by solution fluidized-bed crystallizing and drying at temperature 80 DEG C.Obtain finished product Sunmorl N 60S.With glucose meter, the rate of recovery 90.2%, Sunmorl N 60S purity reaches 99.2%, and the indexs such as vitriol, muriate, reduzate reach food, pharmaceutical grade requirement.
Embodiment 2
In 30L tank, add 20L 35% glucose solution, add 200mL (to 8000U/ml) glucose oxidase simultaneously, 60mL (to 100,000 U/ml) catalase, setting reaction pH is 6.5, and the sodium hydroxide stream with 50% adds adjustment pH.Maintain temperature of reaction 38 DEG C, pass into pressurized air, air flow is 0.8vvm, maintains tank pressure 0.2MPa, and open and stir, rotating speed is 250-300r/min.In 20 hours reaction times, record residual sugar <0.3%, stream adds 50% sodium hydroxide, and to reach 3.11L be now 7.0 by reaction pH regulator, and catalyzed reaction terminates.After reaction terminates, add 600g gac and be heated to the 5min that seethes with excitement, micropore suction filtration obtains colourless solution, the solution obtained by suction filtration, at negative 0.08MPa, is evaporated to and is greater than 70% concentration, by solution fluidized-bed crystallizing and drying at temperature 80 DEG C.Obtain finished product Sunmorl N 60S.With glucose meter, the rate of recovery 92.4%, Sunmorl N 60S purity reaches 99.4%, and the indexs such as vitriol, muriate, reduzate reach food, pharmaceutical grade requirement.
Table 1 Sunmorl N 60S standard QB/T 4484-2013
Note: top grade product can be used for medicine industry, and first grade can be used for foodstuffs industry, seconds and three grades of product can be used for other industry.
Although the present invention with preferred embodiment openly as above; but it is also not used to limit the present invention, any person skilled in the art, without departing from the spirit and scope of the present invention; all can do various changes and modification, what therefore protection scope of the present invention should define with claims is as the criterion.
Claims (10)
1. an enzyme process prepares the method for Sunmorl N 60S, it is characterized in that, by glucose under the catalysis of glucose oxidase, gluconic acid and hydrogen peroxide is produced with oxygen G&W generation oxidizing reaction, hydrogen peroxide is decomposed into water and oxygen under catalatic effect, and gluconic acid then produces Sunmorl N 60S with sodium hydroxide generation neutralization reaction.
2. method according to claim 1, is characterized in that, reaction solution is obtained finished product Sunmorl N 60S through the enzyme that goes out, decolouring, concentrated, crystallizing and drying.
3. method according to claim 1, it is characterized in that, mainly comprise the following steps: in the glucose solution of massfraction 35-40%, once or in batches add glucose oxidase and catalase, stream adds the sodium hydroxide solution of massfraction 40-50% to maintain pH value of solution 5.0-7.0, and holding temperature 38 ± 1 DEG C, passes into pressurized air, air flow is 0.5-1vvm, maintain tank pressure 0.2-0.5MPa, mixing speed is 250-300r/min, reaction 20-24 hour; Record residual sugar <0.3%, stream hydro-oxidation sodium reaches theoretical reaction requirement amount, and be now 6.5-7.5 by reaction pH regulator, after maintenance 20-30min, catalyzed reaction terminates.
4. method according to claim 1 and 2, it is characterized in that, reaction solution is obtained finished product Sunmorl N 60S through the enzyme that goes out, decolouring, concentrated, crystallizing and drying, mainly comprise the following steps: (1) goes out enzyme and decolouring: react after terminating, add gac and heat, filtering and obtain colourless solution; (2) concentrated: will filter the solution obtained, reduction vaporization concentrates, and obtains the solution that Sunmorl N 60S massfraction is greater than 70%; (3) crystallizing and drying: by solution fluidised bed drying.
5. the method according to claim 1 or 3, is characterized in that, glucose oxidase addition is 5000-10000U/ml.
6. the method according to claim 1 or 3, is characterized in that, catalase addition is 10-20 ten thousand U/ml.
7. method according to claim 4, is characterized in that, step (1) is the powdered active carbon adding 2-5% in reaction solution, and ebuillition of heated 20min, then cross and filter protein and pigment.
8. method according to claim 4, is characterized in that, the filtrate through go out enzyme and decolouring at negative 0.07-0.09MPa, is evaporated to gluconic acid na concn and reaches more than 70% by step (2) under the condition that temperature is 80 DEG C.
9. method according to claim 4, is characterized in that, described filtration is micropore suction filtration or Plate Filtration.
10. method according to claim 2, is characterized in that, described crystallizing and drying is that fluidized bed with spraying is dry.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829446A (en) * | 2015-04-17 | 2015-08-12 | 山东西王糖业有限公司 | Method for extracting sodium gluconate without generating mother liquor |
| CN106337065A (en) * | 2016-08-24 | 2017-01-18 | 山东福洋生物科技有限公司 | Technological method for producing sodium gluconate by enzyme method |
| CN106399404A (en) * | 2016-12-08 | 2017-02-15 | 辽阳富强食品化工有限公司 | Production method of calcium gluconate |
| CN106497992A (en) * | 2016-11-23 | 2017-03-15 | 南京工业大学 | A kind of method that high-gravity technology prepares gluconic acid or gluconate |
| CN106978451A (en) * | 2017-03-29 | 2017-07-25 | 华南理工大学 | A kind of method that immobilized glucose oxidase prepares sodium gluconate |
| CN107012176A (en) * | 2017-04-21 | 2017-08-04 | 山东大学 | A kind of method of the conversion production sodium gluconate by material, enzyme method of cellulose biomass |
| CN107973711A (en) * | 2017-11-22 | 2018-05-01 | 山东福洋生物科技有限公司 | A kind of method of Simulation moving bed separating glucose acid mother liquid of sodium |
| CN108336362A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | The preparation method of alloy-coated material |
| CN108336322A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | The preparation method of pole plate creme |
| CN108336324A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | The preparation method of unleaded creme |
| CN108336323A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | Unleaded cladding material |
| CN108336325A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | Pole plate creme |
| CN109022506A (en) * | 2018-08-17 | 2018-12-18 | 青岛中科潮生生物技术有限公司 | The method that sodium gluconate is prepared using lignocellulosic |
| CN109517850A (en) * | 2018-10-08 | 2019-03-26 | 山东西王糖业有限公司 | The method for preparing sodium gluconate as raw material using raffinate after glucose crystallization |
| CN110904164A (en) * | 2019-12-02 | 2020-03-24 | 武汉新华扬生物股份有限公司 | Biocatalysis method for preparing gluconate |
| CN112105378A (en) * | 2018-01-03 | 2020-12-18 | 宾夕法尼亚州研究基金会 | Glucose oxidase composition as anticonvulsant for neonates |
| CN112125935A (en) * | 2020-10-15 | 2020-12-25 | 吉源(淮北)食品科技有限公司 | Preparation method of rhamnose |
| CN116515914A (en) * | 2023-06-25 | 2023-08-01 | 山东福洋生物科技股份有限公司 | Production method for improving quality of sodium gluconate finished product |
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Cited By (21)
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| CN104829446A (en) * | 2015-04-17 | 2015-08-12 | 山东西王糖业有限公司 | Method for extracting sodium gluconate without generating mother liquor |
| CN106337065A (en) * | 2016-08-24 | 2017-01-18 | 山东福洋生物科技有限公司 | Technological method for producing sodium gluconate by enzyme method |
| CN106497992A (en) * | 2016-11-23 | 2017-03-15 | 南京工业大学 | A kind of method that high-gravity technology prepares gluconic acid or gluconate |
| CN106497992B (en) * | 2016-11-23 | 2019-07-19 | 南京工业大学 | A kind of method that high-gravity technology prepares gluconic acid or gluconate |
| CN106399404A (en) * | 2016-12-08 | 2017-02-15 | 辽阳富强食品化工有限公司 | Production method of calcium gluconate |
| CN106978451A (en) * | 2017-03-29 | 2017-07-25 | 华南理工大学 | A kind of method that immobilized glucose oxidase prepares sodium gluconate |
| CN106978451B (en) * | 2017-03-29 | 2020-04-28 | 华南理工大学 | Method for preparing sodium gluconate by immobilized glucose oxidase |
| CN107012176A (en) * | 2017-04-21 | 2017-08-04 | 山东大学 | A kind of method of the conversion production sodium gluconate by material, enzyme method of cellulose biomass |
| CN107012176B (en) * | 2017-04-21 | 2021-01-15 | 山东大学 | Method for producing sodium gluconate by using cellulose biomass as raw material through enzymatic conversion |
| CN107973711A (en) * | 2017-11-22 | 2018-05-01 | 山东福洋生物科技有限公司 | A kind of method of Simulation moving bed separating glucose acid mother liquid of sodium |
| CN108336323A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | Unleaded cladding material |
| CN108336325A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | Pole plate creme |
| CN108336324A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | The preparation method of unleaded creme |
| CN108336322A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | The preparation method of pole plate creme |
| CN108336362A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | The preparation method of alloy-coated material |
| CN112105378A (en) * | 2018-01-03 | 2020-12-18 | 宾夕法尼亚州研究基金会 | Glucose oxidase composition as anticonvulsant for neonates |
| CN109022506A (en) * | 2018-08-17 | 2018-12-18 | 青岛中科潮生生物技术有限公司 | The method that sodium gluconate is prepared using lignocellulosic |
| CN109517850A (en) * | 2018-10-08 | 2019-03-26 | 山东西王糖业有限公司 | The method for preparing sodium gluconate as raw material using raffinate after glucose crystallization |
| CN110904164A (en) * | 2019-12-02 | 2020-03-24 | 武汉新华扬生物股份有限公司 | Biocatalysis method for preparing gluconate |
| CN112125935A (en) * | 2020-10-15 | 2020-12-25 | 吉源(淮北)食品科技有限公司 | Preparation method of rhamnose |
| CN116515914A (en) * | 2023-06-25 | 2023-08-01 | 山东福洋生物科技股份有限公司 | Production method for improving quality of sodium gluconate finished product |
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