CN111172205B - Method for producing glucose lactone by using bipolar membrane electrodialysis device - Google Patents
Method for producing glucose lactone by using bipolar membrane electrodialysis device Download PDFInfo
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- CN111172205B CN111172205B CN201911414114.XA CN201911414114A CN111172205B CN 111172205 B CN111172205 B CN 111172205B CN 201911414114 A CN201911414114 A CN 201911414114A CN 111172205 B CN111172205 B CN 111172205B
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- 239000012528 membrane Substances 0.000 title claims abstract description 99
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 16
- 239000008103 glucose Substances 0.000 title claims abstract description 16
- -1 glucose lactone Chemical class 0.000 title claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 238000000855 fermentation Methods 0.000 claims abstract description 28
- 230000004151 fermentation Effects 0.000 claims abstract description 28
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 27
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims abstract description 17
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims abstract description 16
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 239000000174 gluconic acid Substances 0.000 claims abstract description 15
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 15
- 238000005341 cation exchange Methods 0.000 claims abstract description 14
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 13
- 235000012207 sodium gluconate Nutrition 0.000 claims abstract description 13
- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004366 Glucose oxidase Substances 0.000 claims abstract description 10
- 108010015776 Glucose oxidase Proteins 0.000 claims abstract description 10
- 229920001429 chelating resin Polymers 0.000 claims abstract description 10
- 229940116332 glucose oxidase Drugs 0.000 claims abstract description 10
- 235000019420 glucose oxidase Nutrition 0.000 claims abstract description 10
- 102000016938 Catalase Human genes 0.000 claims abstract description 8
- 108010053835 Catalase Proteins 0.000 claims abstract description 8
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 239000013522 chelant Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 206010011703 Cyanosis Diseases 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 101000972449 Homo sapiens Sperm-egg fusion protein LLCFC1 Proteins 0.000 description 2
- 102100022736 Sperm-egg fusion protein LLCFC1 Human genes 0.000 description 2
- 235000013527 bean curd Nutrition 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 102000003992 Peroxidases Human genes 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 235000012209 glucono delta-lactone Nutrition 0.000 description 1
- 229960003681 gluconolactone Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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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
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
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- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for producing glucose lactone by using a bipolar membrane electrodialysis device, which comprises the following steps: (1) Adding glucose solution, glucose oxidase and catalase into a fermentation tank for fermentation to obtain fermentation liquor containing sodium gluconate; (2) Pretreating fermentation liquor, wherein the pretreatment comprises microporous filtration, ceramic membrane treatment or ultrafiltration treatment and chelating resin treatment in sequence; (3) Carrying out electrodialysis treatment on the pretreated feed liquid in the step (2) by using a two-compartment bipolar membrane electrodialysis device provided with a bipolar membrane and a cation exchange membrane, and respectively obtaining a gluconic acid solution and a sodium hydroxide solution in a feed liquid chamber and an alkali liquid chamber; (4) Treating the gluconic acid solution obtained in the step (3) with cation exchange resin; (5) Evaporating and crystallizing the gluconic acid solution treated in the step (4) to obtain the glucolactone. The invention can shorten the process route, reduce the energy consumption and the wastewater discharge and reduce the production cost.
Description
Technical Field
The invention relates to a production method of glucolactone.
Background
The glucose lactone is mainly used as a bean curd coagulant for producing bean curd, and can also be used in the fields of milk coagulants, quality improvers, acidulants and the like. The traditional process mainly comprises the steps of microbial fermentation, filter pressing by a filter press, active carbon decoloration, evaporation concentration to obtain sodium gluconate solid, solution preparation, treatment by ion exchange resin, concentration and crystallization to obtain the lactone. The traditional process flow is long, active carbon is needed for decoloring, sodium gluconate is evaporated and concentrated into sodium gluconate crystals, then the sodium gluconate crystals are dissolved, the sodium gluconate crystals are converted into gluconic acid by using cation exchange resin, the gluconolactone is concentrated and crystallized, the twice evaporation and concentration are needed, the evaporation energy consumption is high, meanwhile, in the step of converting the ion exchange resin into gluconic acid, the step of regenerating by using acid and the step of flushing by using water are needed, a large amount of acid wastewater is generated, and after neutralization by using alkali, brine with COD exceeding the standard is generated, and the brine is difficult to treat and causes environmental pollution.
Disclosure of Invention
Aiming at the defects of the traditional process for producing the glucose lactone, the invention aims to provide a production method of the glucose lactone, so as to shorten the process route, reduce the energy consumption and the wastewater discharge and reduce the production cost.
The invention adopts the technical scheme that:
a clean production process of glucose lactone, which comprises the following steps:
(1) Adding glucose solution, glucose oxidase and catalase into a fermentation tank, continuously adding sodium hydroxide solution to adjust the pH value of the system to be 3.5-4.5, and controlling the temperature to be 30-40 ℃ for full fermentation to obtain fermentation liquor containing sodium gluconate;
(2) Pretreating the fermentation liquor obtained in the step (1), wherein the pretreatment comprises microporous filtration, ceramic membrane treatment or ultrafiltration treatment and chelating resin treatment in sequence;
(3) Carrying out electrodialysis treatment on the pretreated feed liquid in the step (2) by using a bipolar membrane electrodialysis device with two compartments (alkali liquor chamber/feed liquor chamber) provided with a bipolar membrane and a cation exchange membrane, and respectively obtaining a gluconic acid solution and a sodium hydroxide solution in the feed liquor chamber and the alkali liquor chamber, wherein the sodium hydroxide solution is used for regulating the pH value of a fermentation system in the step (1);
(4) Treating the gluconic acid solution obtained in the step (3) with cation exchange resin to remove sodium ions;
(5) Evaporating and crystallizing the gluconic acid solution treated in the step (4) to obtain the glucolactone.
In the step (1), glucose is oxidized by glucose oxidase, hydrogen peroxide is generated in the process, the hydrogen peroxide has certain toxicity to the glucose oxidase, and the hydrogen peroxide is decomposed into water and oxygen by adding hydrogen peroxidase, so that the oxidation reaction is continued, and meanwhile, a sodium hydroxide solution with a certain concentration is slowly added, the pH value of the environment is maintained, and the activity of the enzyme is protected. Preferably, the concentration of the glucose solution is 25wt% to 60wt%. Preferably, the concentrations of glucose oxidase and catalase in the fermentation system are 0.3 to 0.5wt% and 0.2 to 0.5wt%, respectively. Preferably, the pH of the system is controlled between 3.5 and 4.5, and fermentation is carried out for 20 to 40 hours at a temperature between 30 and 40 ℃ to obtain fermentation liquor. The glucose oxidase and catalase may be added in portions.
In the step (2) of the present invention, it is preferable that the pore size of the filter element of the microporous filter used for the microporous filtration is 1 to 5. Mu.m.
In the step (2), the purpose of the ceramic membrane treatment or ultrafiltration treatment is to filter out protein matters in the solution. Preferably, the ceramic membrane treatment adopts a ceramic membrane with the thickness of 20-100nm and the operating pressure is 0.1-0.4Mpa. Preferably, the ultrafiltration membrane adopted in the ultrafiltration treatment is a hollow fiber membrane or a coiled ultrafiltration membrane, the molecular weight cut-off of the adopted ultrafiltration membrane is 1000-50000, the membrane has good pollution resistance and fouling resistance, and the operation pressure of the ultrafiltration treatment is 0.1-0.4Mpa.
In step (2) of the present invention, the chelating resin treatment is aimed at removing polyvalent metal ions in the fermentation broth, so that it is preferable to use a polyvalent cation chelating resin such as: CH-93, LSC-500, etc., the chelating resin is used for the preparation of polyvalent cations (such as Ca 2+ ，Mg 2+ ,Fe 2+ ,Fe 3+ Etc.) has a strong adsorption capacity.
In the step (3) of the invention, the bipolar membrane electrodialysis device provided with bipolar membranes and cation exchange membranes comprises a direct current power supply, an anode plate connected with the anode of the power supply, a cathode plate connected with the cathode of the direct current power supply and a membrane stack arranged between the anode plate and the cathode plate, wherein the membrane stack is formed by sequentially arranging and assembling the bipolar membranes and the cation exchange membranes at intervals, the outermost membranes are bipolar membranes, two adjacent membranes are separated by a separator, and an electrodialysis unit with two compartments (alkali liquor chamber/feed liquor chamber) is formed by an adjacent group of bipolar membranes, cation exchange membranes and bipolar membranes; a polar liquid chamber is formed between the anode plate and the cathode plate and the adjacent bipolar membrane respectively; the alkali liquor chamber is externally connected with an alkali liquor tank and forms a loop through a circulating pump; the feed liquid chamber is externally connected with a feed liquid tank and forms a loop through a circulating pump; the polar liquid chambers are respectively externally connected with a polar liquid tank and form a loop through a circulating pump.
The step (3) is specifically implemented as follows: the pretreated fermentation liquor is introduced into a feed liquor chamber of the bipolar membrane electrodialysis device, pure water is introduced into the feed liquor chamber, sodium sulfate solution is introduced into a polar liquor chamber, and a circulating pump is started to fill liquor into a membrane stackAnd (3) circulating the solution, turning on a power supply to carry out electrodialysis treatment, generating sodium hydroxide in an alkali liquor chamber, and generating gluconic acid in the feed liquor chamber. The membranes can be screened and the appropriate electrodialysis operating conditions set by those skilled in the art according to the circumstances. In general, the membranes of electrodialysis devices are screened according to membrane stack resistance and current efficiency, preferably lower resistance and higher current efficiency, which means lower process cost; the electrodialysis condition is determined according to the properties of feed liquid and membrane resistance, and corresponding voltage and current are selected in the limiting current density. Preferably, the bipolar membrane is selected from bipolar membranes produced by fumatech, germany, the cation exchange membrane is selected from cation exchange membranes produced by Zhejiang Sai blue Membrane technologies Co., ltd, and the membrane stack consists of 50-200 groups of electrodialysis units. Preferably, the electrodialysis conditions are: controlling the current density of the direct current electric field to be 100-600A/m 2 When the liquid conductivity in the feed liquid chamber is reduced to 3-5 ms/cm, the pH is reduced to 2-2.3, the operation is stopped, the feed liquid chamber obtains the mixed solution of gluconic acid and sodium gluconate, the conversion rate of sodium gluconate reaches above 85-95%, the current efficiency reaches about 70%, and the alkali liquid chamber obtains the sodium hydroxide solution with the concentration of 6-10%.
In the step (4) of the present invention, the cation exchange resin is preferably a strong acid cation exchange resin, such as 001× 2.5,001 ×4, 001× 7,001 × 8,001 ×10, etc., and the residual sodium ions are removed by resin adsorption, so that the sodium ions are removed to meet the crystallization requirement.
In step (5) of the present invention, the evaporative crystallization is preferably carried out in an MVR evaporator. Compared with the prior art, the invention has the beneficial effects that: the invention shortens the process route, realizes clean production, reduces energy consumption, reduces wastewater discharge, and can recycle the byproduct alkali at the same time so as to achieve the purpose of reducing production cost.
Drawings
FIG. 1 is a process flow diagram of the glucolactone of the present invention;
FIG. 2 is a schematic diagram of a principle of producing gluconic acid by bipolar membrane electrodialysis;
FIG. 3 is a schematic flow chart of bipolar membrane electrodialysis for converting sodium gluconate.
Detailed description of the preferred embodiments
The following examples are provided to further illustrate the technical scheme of the present invention, but the scope of the present invention is not limited thereto:
the schematic diagrams of the bipolar membrane electrodialysis device used in the embodiment of the invention are shown as 2 and 3, the bipolar membrane electrodialysis device comprises a direct current power supply, an anode plate connected with the anode of the power supply, a cathode plate connected with the cathode of the direct current power supply and a membrane stack arranged between the anode plate and the cathode plate, the membrane stack is formed by sequentially and alternately arranging and assembling bipolar membranes and cation exchange membranes, the outermost membranes are bipolar membranes, two adjacent membranes are separated by a separator, and an electrodialysis unit with two compartments (alkali liquor chamber/feed liquor chamber) is formed by an adjacent group of bipolar membranes, cation exchange membranes and bipolar membranes; a polar liquid chamber is formed between the anode plate and the cathode plate and the adjacent bipolar membrane respectively; the alkali liquor chamber is externally connected with an alkali liquor tank and forms a loop through a circulating pump; the feed liquid chamber is externally connected with a feed liquid tank and forms a loop through a circulating pump; the polar liquid chambers are respectively externally connected with a polar liquid tank and form a loop through a circulating pump.
Example 1
5t of a 50wt% glucose solution was slowly added to 10m 3 20kg glucose oxidase and 15kg catalase were slowly added simultaneously to the fermenter, and the added enzymes were all from the Tianjin Norwesternase preparation company, and 25% -32% sodium hydroxide solution was continuously added to adjust the pH, and the pH was controlled at 5, and the temperature was controlled at 40 ℃. Fermenting for 24 hr, pumping the fermented liquid through 1 micrometer microporous filter to 5m 3 Ultrafiltration circulation water tank. The ultrafiltration device is a set of Chinese type equipment, the selected membrane is polysulfone hollow fiber membrane with 5 ten thousand size of molecular weight cut-off, the operation pressure is 0.3MPa, and the flux is 0.5m 3 And/h, the ultrafiltration recovery rate reaches 98%. Ultrafiltered permeate is pumped into a feed liquid chamber of a bipolar membrane electrodialysis system after passing through a CH-93 type chelating resin tank, pure water is added into the feed liquid chamber, and 3% sulfur is added into a polar liquid chamberSodium acid solution, the membrane stack of the bipolar membrane electrodialysis system is a two-compartment membrane stack with a width of 400 mm and a length of 800mm and a height of 800mm (effective area of 15m 2 ) The membrane stack consisted of 50 groups of electrodialysis units. The bipolar membrane used was a bipolar membrane from the Fumatech inlet of Germany, and the cation exchange membrane was selected from the group consisting of the cation exchange membranes CTM-1 produced by the company Cyanose. The circulating pump of each compartment is opened, and the flow is controlled to be 3-5m 3 After 2min, the DC power supply is turned on to control the current density to 300A/m 2 When the electric conduction of the feed liquid is reduced to 5ms/cm and the pH=2.3, the reaction is stopped for 8 hours, and the conversion rate of the sodium gluconate reaches 95.5 percent. And then the solution in the feed liquid chamber is pumped into a 001 x 7 strong acid type ion exchange resin tank, and then is pumped into an MVR concentration crystallization tank, and the temperature is controlled to be 60-80 ℃ and the product with the purity of more than 99% is obtained after 48h crystallization.
Example 2
This example is essentially the same as example 1, and the pH in the fermentation described on this basis is controlled at 4.5. The subsequent steps are the same as in example 1, and finally, 1.55t of product is obtained, and the purity is more than 99%.
Example 3
This example is essentially the same as example 1, and the temperature in the fermentation described on this basis is controlled at 35 ℃. The subsequent procedure is the same as in example 1, finally obtaining 1.5t of product with purity >99%.
Example 4
This example is essentially the same as example 1, on the basis of which the ultrafiltration system employs a mesoporous ultrafiltration membrane with a molecular weight cut-off of 10000. The subsequent procedure is the same as in example 1, finally obtaining 1.5t of product with purity >99%.
Example 5
This example is essentially the same as example 1, on the basis of which the ultrafiltration system employs a roll-type ultrafiltration membrane having a molecular weight cut-off of 30000. The subsequent procedure is the same as in example 1, finally obtaining 1.54t of product with purity >99%.
Example 6
The present example is substantially the same as example 2, and the ultrafiltration system employs a roll-type ultrafiltration membrane having a molecular weight cut-off of 10000.
Example 7
30t of a 50% glucose solution was slowly added to 50m 3 120kg glucose oxidase and 120kg catalase were added simultaneously to the fermenter, and sodium hydroxide solution was continuously added to adjust the pH to 4.5, and the temperature was controlled at 40 ℃. After 24h fermentation, the fermentation broth was pumped through a 1 micron microporous filter and into an ultrafiltration circulation tank. The ultrafiltration equipment is industrial equipment of 8040, the selected membrane is a coiled ultrafiltration membrane with a molecular weight cut-off of 3 ten thousand, the operation pressure is 0.4MPa, the flux is 2m < 3 >/h, and the ultrafiltration recovery rate reaches 97.5%. Ultrafiltered permeate is pumped into a feed liquid water tank of a bipolar membrane electrodialysis system after passing through a CH-93 type chelating resin tank, pure water is added into an alkali chamber, 3% sodium sulfate solution is added into a polar liquid chamber, and a two-compartment membrane stack (effective area is 25 m) with membrane stacks of 500 x 1100mm x 400 of the bipolar membrane electrodialysis system 2 ). The membrane stack consisted of 50 groups of electrodialysis units. The bipolar membrane used was a bipolar membrane from the Fumatech inlet of Germany, and the cation exchange membrane was selected from the group consisting of the cation exchange membranes CTM-1 produced by the company Cyanose. The circulating pump of each compartment is opened, and the flow is controlled to be 3-5m 3 After 2min, the DC power supply is turned on to control the current density to 300A/m 2 Stopping the reaction when the electric conduction of the feed liquid is reduced to 3ms/cm and the pH=2, and reacting for 20 hours, wherein the conversion rate of the sodium gluconate reaches 95.2%. Then the solution in the feed liquid chamber is pumped into a 001 x 7 strong acid type ion exchange resin tank, and then is pumped into an MVR concentration crystallization tank, and the temperature is controlled to be 60-80 ℃ for 48 hours to obtain 10t product with purity>99％。
Taking example 1 of the present invention as an example, the energy consumption and cost of producing one ton of glucolactone were compared with those of the conventional process, and the results are shown in the following table:
TABLE 1
| Name of the name | Traditional process | The process |
| Cost per ton of energy consumption | 1000 yuan | 750 yuan |
| Ton of waste water | 13 ton of | 1 ton of |
| Cost per ton | 6300 yuan | 5200 |
Therefore, the clean production process can reduce the energy consumption cost by more than 20%, reduce the wastewater discharge by more than 90%, reduce the production cost by more than 15%, and has remarkable progress.
Claims (10)
1. The production method of the glucose lactone comprises the following steps:
(1) Adding glucose solution, glucose oxidase and catalase into a fermentation tank, continuously adding sodium hydroxide solution to adjust the pH value of the system to be 3.5-4.5, and controlling the temperature to be 30-40 ℃ for full fermentation to obtain fermentation liquor containing sodium gluconate;
(2) Pretreating the fermentation liquor obtained in the step (1), wherein the pretreatment sequentially comprises microporous filtration, ceramic membrane treatment or ultrafiltration treatment and chelating resin treatment;
(3) Carrying out electrodialysis treatment on the pretreated feed liquid in the step (2) by using a two-compartment bipolar membrane electrodialysis device provided with a bipolar membrane and a cation exchange membrane, and respectively obtaining a gluconic acid solution and a sodium hydroxide solution in a feed liquid chamber and an alkali liquid chamber, wherein the sodium hydroxide solution is used for regulating the pH value of a fermentation system in the step (1);
(4) Treating the gluconic acid solution obtained in the step (3) with cation exchange resin to remove sodium ions;
(5) Evaporating and crystallizing the gluconic acid solution treated in the step (4) to obtain the glucolactone.
2. The method for producing a glucolactone according to claim 1, wherein: in the step (1), the concentration of the glucose solution is 25-60 wt%, so that the concentration of glucose oxidase and catalase in a fermentation system is 0.3-0.5 wt% and 0.2-0.5 wt% respectively, and the pH of the system is controlled to be 3.5-4.5, and the temperature is 30-40 ℃ for fermentation for 20-40 hours, thus obtaining the fermentation liquid.
3. The method for producing a glucolactone according to claim 1, wherein: in the step (2), the pore diameter of the filter core of the microporous filter adopted by the microporous filter is 1-5 mu m.
4. The method for producing a glucolactone according to claim 1, wherein: in the step (2), the ceramic membrane treatment adopts a ceramic membrane with the thickness of 20-100nm, and the operating pressure is 0.1-0.4Mpa.
5. The method for producing a glucolactone according to claim 1, wherein: the ultrafiltration membrane adopted in the ultrafiltration treatment is a hollow fiber membrane or a coiled ultrafiltration membrane, the molecular weight cut-off of the adopted ultrafiltration membrane is 1000-50000, and the operation pressure of the ultrafiltration treatment is 0.1-0.4Mpa.
6. The method for producing a glucolactone according to claim 1, wherein: in step (2), the chelating resin treatment uses a multivalent cation chelating resin.
7. The method for producing a glucolactone according to claim 6, wherein: in the step (2), the multivalent cation chelate resin is CH-93 or LSC-500.
8. The method for producing a glucolactone according to claim 1, wherein: the step (3) is specifically implemented as follows: the pretreated fermentation liquor is introduced into a feed liquor chamber of the bipolar membrane electrodialysis device, pure water is introduced into the feed liquor chamber, sodium sulfate solution is introduced into a polar liquor chamber, a circulating pump is started to enable the membrane stack to be full of liquid and circulate, a power supply is started to carry out electrodialysis treatment, sodium hydroxide is generated in the feed liquor chamber, and gluconic acid is generated in the feed liquor chamber.
9. The method for producing a glucolactone according to claim 1, wherein: in the step (3), the membrane stack of the bipolar membrane electrodialysis device consists of 50-200 groups of electrodialysis units, and the electrodialysis conditions are as follows: controlling the current density of the direct current electric field to be 100-600A/m 2 Controlling the temperature at 5-40 ℃, and stopping the operation when the liquid conductivity in the liquid chamber is reduced to 3-5 ms/cm and the pH is reduced to 2-2.3.
10. The method for producing a glucolactone according to claim 1, wherein: in the step (4), the cation exchange resin is a strong acid type cation exchange resin.
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