CN104450806B - A kind of method that enzyme process prepares sodium gluconate - Google Patents
A kind of method that enzyme process prepares sodium gluconate Download PDFInfo
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- CN104450806B CN104450806B CN201410707720.1A CN201410707720A CN104450806B CN 104450806 B CN104450806 B CN 104450806B CN 201410707720 A CN201410707720 A CN 201410707720A CN 104450806 B CN104450806 B CN 104450806B
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- sodium gluconate
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/58—Aldonic, ketoaldonic or saccharic acids
Abstract
The invention discloses a kind of method that enzyme process prepares sodium gluconate, belong to technological field of biochemistry.The present invention is by glucose under the catalysis of glucose oxidase, oxidation reaction production gluconic acid and hydrogen peroxide occurs with oxygen and water, hydrogen peroxide is decomposed into water and oxygen in the presence of catalase, and neutralization reaction production sodium gluconate then occurs with sodium hydroxide for gluconic acid；Through enzyme deactivation, decolouring, concentration, crystallize, be dried to obtain finished product sodium gluconate.The present invention can be used for the sodium gluconate for producing food-grade and pharmaceutical grade, have the advantages that simple to operate, the reaction time is short, and product purity is high, and waste is few.
Description
Technical field
The present invention relates to a kind of method that enzyme process prepares sodium gluconate, belong to technological field of biochemistry.
Background technology
Sodium gluconate is a kind of organic acid salt of multihydroxyl, is widely used in the industries such as chemical industry, food, medicine, building.Mesh
The production method of preceding sodium gluconate mainly has eletrooxidation method, electrolytic oxidation, heterogeneous catalytic oxidation method and biology hair
Four kinds of methods such as ferment method.Eletrooxidation method is using crystal glucose as raw material, is added after crystal glucose is dissolved in water
Catalyst, under certain reaction temperature, add people liquor natrii hypochloritis, while alkali lye is added dropwise to make equilibrium system to sodium gluconate
Generation direction movement, reaction terminate after, sodium gluconate product is produced by condensing crystallizing.The technical process is easily manipulated,
But sodium gluconate low yield, sodium chloride as impurity can be mixed with product, the application of product is restricted.Electrolytic oxidation is to be based on
The principle of electrochemistry, is previously added a certain amount of glucose solution and suitable electrolyte in a cell, controlling reaction temperature,
Then cell reaction is carried out to the constant electric current of electrolytic cell people, after electrolysis terminates, electrolyte condensing crystallizing is produced into gluconic acid
Sodium crystal.Electrolytic oxidation production cost is higher, and equipment is complicated, and reaction should not control, and not be suitable for industrialized production.Multiphase is urged
It is in retort plus the certain density glucose solution of people and catalyst to change oxidizing process, then is passed through into reaction system appropriate
Air, after controlling constant reaction temperature and pH, reaction to terminate, filtered, condensing crystallizing, centrifugal drying obtain sodium gluconate
Crystal.The technique is simple, and product quality is preferable, but catalyst cost is higher.Biological fermentation process is to add a large amount of trainings with seed liquor
Support base and carry out fermenting and producing sodium gluconate.Higher concentration of substrate can be resistant to the seed selection of excellent species.But
Because the addition of substantial amounts of culture medium and accessory substance bring very burden to the Hydrolysis kinetics in later stage, the matter of product is directly influenced
Amount and conversion ratio.
The content of the invention
The present invention provides a kind of method by enzyme Direct Catalytic Oxidation glucose production sodium gluconate, overcomes existing life
Technical disadvantages are produced, there is the advantages that transformation efficiency is high, and the production time is short, and product purity is high, and technique is simple.
The technical scheme is that by glucose under the catalysis of glucose oxidase, it is anti-that oxidation occurs with oxygen and water
Gluconic acid and hydrogen peroxide should be produced, hydrogen peroxide is decomposed into water and oxygen in the presence of catalase, and grape
Neutralization reaction production sodium gluconate then occurs with sodium hydroxide for saccharic acid.Further, through enzyme deactivation, decolouring, concentration, crystallization, drying
Obtain finished product sodium gluconate.
The enzymic catalytic reaction equation is：
4C6H12O6+3O2+2H2O→4C6H12O7+2H2O2
H2O2→2H2O+O2
C6H12O7+NaOH→C6H11O7Na+H2O
The invention mainly includes steps：(1) enzyme reaction：Into mass fraction 35-40% glucose solution once
Or glucose oxidase and catalase is added portionwise, stream plus mass fraction 40-50% sodium hydroxide solution are to maintain
PH value of solution 5.0-7.0,38 ± 1 DEG C of temperature is maintained, be passed through compressed air, throughput 0.5-1vvm, maintain tank pressure 0.2-
0.5MPa, speed of agitator 250-300r/min, hour in reaction time 20-24；Measure residual sugar<0.3%, stream hydrogenation sodium oxide molybdena reaches
To theoretical reaction requirement amount, and it is 6.5-7.5 to adjust pH, and after maintaining 20-30min, catalytic reaction terminates.(2) enzyme deactivation is with decolourizing：
After reaction terminates, add activated carbon and heat, be filtrated to get colourless solution.(3) concentrate：By the solution obtained by filtering, decompression
It is concentrated by evaporation, obtains the solution that sodium gluconate mass fraction is more than 70%.(4) crystallizing and drying：By solution fluidized bed drying.
In one embodiment of the invention, step (1) glucose oxidase addition is 5000-10000U/ml, mistake
Hydrogen oxide enzyme addition is the U/ml of 10-20 ten thousand.
In another embodiment of the invention, step (1) glucose oxidase addition is 6000U/ml, peroxidating
Hydrogen enzyme addition is 100,000 U/ml.
In one embodiment of the invention, step (1) the reaction end refers to working as residual sugar in course of reaction<
0.3%, flow the sodium hydroxide solution added and reach theoretical addition, regulation pH is 6.5-7.5 and maintains a period of 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 that 2-5% powdered active carbon is added into reaction solution,
And ebuillition of heated 5-20min, then it is filtered to remove protein and pigment.The filtering can be suction filtration or plate-frame filtering.
In one embodiment of the invention, step (3) will pass through enzyme deactivation and the filtrate decolourized in negative 0.07-
0.09MPa, gluconic acid na concn is concentrated under reduced pressure into up to more than 70% at 80 DEG C of temperature.
Sodium gluconate drying crystalline final content produced by the present invention>99.4%, it is more than with the glucose meter rate of recovery
90%, and reach primes and top grade product standard.This invention simplifies production technology, more existing production method is compared to investment
Few, utilization rate of equipment and installations is high, with short production cycle, and the impurity introduced in course of reaction is few, accessory substance is few, and the purification processes in later stage are non-
It is often simple, the high sodium gluconate of purity can be obtained.
Brief description of the drawings
Fig. 1 technological process of productions of the present invention
Embodiment
Embodiment 1
The glucose solutions of 20L 40% are added in 30L tanks, while it is glycoxidative to add 150mL (to 6000U/ml) grape
Enzyme, 75 (to 100,000 U/ml) mL catalases set reaction pH as 6.0, add regulation pH with 50% sodium hydroxide stream, maintain
38 DEG C of reaction temperature, compressed air is passed through, throughput 0.5vvm, tank pressure 0.2MPa is maintained, opens stirring, rotating speed 250-
300r/min.Reaction about 24 hours, measures residual sugar<0.3%, stream plus 50% sodium hydroxide reach 3.56L, and will reaction pH regulations
For 7.0, half an hour is maintained, catalytic reaction terminates.After reaction terminates, add 600g activated carbons and be heated to the 5min that seethes with excitement, micropore
Suction filtration obtains colourless solution, and the solution obtained by filtering is concentrated under reduced pressure into more than 70% at negative 0.08MPa, 80 DEG C of temperature
Concentration, by solution fluid bed crystallizing and drying.Obtain finished product sodium gluconate.With glucose meter, the rate of recovery 90.2%, gluconic acid
Sodium purity reaches 99.2%, and the index such as sulfate, chloride, reduzate reaches food, pharmaceutical grade requirement.
Embodiment 2
The glucose solutions of 20L 35% are added in 30L tanks, while it is glycoxidative to add 200mL (to 8000U/ml) grape
Enzyme, 60mL (to 100,000 U/ml) catalase set reaction pH as 6.5, add regulation pH with 50% sodium hydroxide stream.Maintain
38 DEG C of reaction temperature, compressed air is passed through, throughput 0.8vvm, tank pressure 0.2MPa is maintained, opens stirring, rotating speed 250-
300r/min.In 20 hours reaction time, measure residual sugar<0.3%, stream plus 50% sodium hydroxide reach 3.11L and will now react pH
7.0 are adjusted to, catalytic reaction terminates.After reaction terminates, add 600g activated carbons and be heated to the 5min that seethes with excitement, micropore filters to obtain
Colourless solution, the solution obtained by filtering is concentrated under reduced pressure at negative 0.08MPa, 80 DEG C of temperature more than 70% concentration, will be molten
Liquid fluid bed crystallizing and drying.Obtain finished product sodium gluconate.With glucose meter, the rate of recovery 92.4%, sodium gluconate purity reaches
To 99.4%, the index such as sulfate, chloride, reduzate reaches food, pharmaceutical grade requirement.
The sodium gluconate standard QB/T 4484-2013 of table 1
Note：Top grade product can be used for medical industry, and primes can be used for food industry, and seconds and three-level product can be used for other
Industry.
Although the present invention is disclosed as above with preferred embodiment, it is not limited to the present invention, any to be familiar with this skill
The people of art, without departing from the spirit and scope of the present invention, it can all do various change and modification, therefore the protection model of the present invention
Enclose being defined of being defined by claims.
Claims (2)
1. a kind of method that enzyme process prepares sodium gluconate, it is characterised in that it is molten that the glucose of 20L 40% is added in 30L tanks
Liquid, while add 150mL glucose oxidases to 6000U/mL, 75mL catalases to 100,000 U/mL, set reaction pH as
6.0, regulation pH is added with 50% sodium hydroxide stream, 38 DEG C of maintenance reaction temperature is passed through compressed air, throughput 0.5vvm,
Tank pressure 0.2MPa is maintained, opens stirring, rotating speed 250-300r/min；Reaction 24 hours, measures residual sugar<0.3%, stream plus 50%
Sodium hydroxide reaches 3.56L, and reaction pH is adjusted into 7.0, maintains half an hour, catalytic reaction terminates；After reaction terminates, add
600g activated carbons are simultaneously heated to the 5min that seethes with excitement, and micropore filters to obtain colourless solution, and the solution obtained by filtering is being born
0.08MPa, it is concentrated under reduced pressure into more than 70% concentration at 80 DEG C of temperature, by solution fluid bed crystallizing and drying, obtains finished product glucose
Sour sodium.
2. a kind of method that enzyme process prepares sodium gluconate, it is characterised in that it is molten that the glucose of 20L 35% is added in 30L tanks
Liquid, while add 200mL glucose oxidases to 8000U/mL, 60mL catalases to 100,000 U/mL, set reaction pH as
6.5, regulation pH is added with 50% sodium hydroxide stream；38 DEG C of maintenance reaction temperature, is passed through compressed air, throughput 0.8vvm,
Tank pressure 0.2MPa is maintained, opens stirring, rotating speed 250-300r/min；In 20 hours reaction time, measure residual sugar<0.3%, stream adds
50% sodium hydroxide reaches 3.11L and reaction pH now is adjusted into 7.0, and catalytic reaction terminates；After reaction terminates, add 600g and live
Property charcoal and be heated to the 5min that seethes with excitement, micropore filters to obtain colourless solution, the solution obtained by filtering, in negative 0.08MPa, temperature
It is concentrated under reduced pressure at 80 DEG C more than 70% concentration, by solution fluid bed crystallizing and drying, obtains finished product sodium gluconate.
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Families Citing this family (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 |
| 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 |
| CN106978451B (en) * | 2017-03-29 | 2020-04-28 | 华南理工大学 | Method for preparing sodium gluconate by immobilized glucose oxidase |
| 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 |
| 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 |
| CN108336325A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | 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 |
| CN108336323A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | Unleaded cladding material |
| WO2019136168A1 (en) * | 2018-01-03 | 2019-07-11 | Penn State Research Foundation | Glucose oxidase compositions as a neonate anticonvulsant |
| CN109022506B (en) * | 2018-08-17 | 2021-04-27 | 青岛中科潮生生物技术有限公司 | Method for preparing sodium gluconate by adopting lignocellulose |
| 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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Inventor after: Yu Xiaobin Inventor after: Xiao Chengjian Inventor after: Gu Qiuya Inventor before: Yu Xiaobin Inventor before: Xiao Chengjian |
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