CN111172205A - Method for producing gluconolactone by using bipolar membrane electrodialysis device - Google Patents
Method for producing gluconolactone by using bipolar membrane electrodialysis device Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 101
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 35
- 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 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 235000012209 glucono delta-lactone Nutrition 0.000 title claims description 17
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- 239000007788 liquid Substances 0.000 claims abstract description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000000855 fermentation Methods 0.000 claims abstract description 34
- 230000004151 fermentation Effects 0.000 claims abstract description 34
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 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
- 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 16
- 239000000174 gluconic acid Substances 0.000 claims abstract description 16
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 16
- 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
- 108010015776 Glucose oxidase Proteins 0.000 claims abstract description 10
- 239000004366 Glucose oxidase Substances 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 9
- 108010053835 Catalase Proteins 0.000 claims abstract description 9
- 229920001429 chelating resin Polymers 0.000 claims abstract description 9
- 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 claims abstract description 8
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 238000001471 micro-filtration Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000005086 pumping Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- -1 Ca)2+ Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- UKLJMHXGZUJRTL-UHFFFAOYSA-L calcium;n-cyclohexylsulfamate Chemical compound [Ca+2].[O-]S(=O)(=O)NC1CCCCC1.[O-]S(=O)(=O)NC1CCCCC1 UKLJMHXGZUJRTL-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 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
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000463 material Substances 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
- 239000003607 modifier 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
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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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Abstract
The invention discloses a method for producing glucolactone by using a bipolar membrane electrodialysis device, which comprises the following steps: (1) adding a 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 sequentially comprises microfiltration, ceramic membrane treatment or ultrafiltration treatment and chelating resin treatment; (3) carrying out electrodialysis treatment on the feed liquid pretreated in the step (2) by using a two-compartment bipolar membrane electrodialysis device provided with a bipolar membrane and a cation exchange membrane, and obtaining a gluconic acid solution and a sodium hydroxide solution in a feed liquid chamber and an alkali liquor chamber respectively; (4) treating the gluconic acid solution obtained in the step (3) by using cation exchange resin; (5) and (4) 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 waste water discharge and reduce the production cost.
Description
Technical Field
The invention relates to a method for producing glucolactone.
Background
The gluconolactone is mainly used as a bean curd coagulant for producing bean curd, and also can be used in the fields of milk coagulants, quality modifiers, acidulants and the like. The traditional production method is mainly prepared by microbial fermentation, and comprises the steps of filter pressing by a filter press, decoloring by active carbon, evaporating and concentrating to obtain sodium gluconate solid, preparing a solution, treating by ion exchange resin, concentrating and crystallizing to obtain lactone. The traditional process has long flow, active carbon is required for decoloring, sodium gluconate is evaporated and concentrated to form sodium gluconate crystals, the sodium gluconate crystals are dissolved again, cation exchange resin is used for converting the sodium gluconate crystals into gluconic acid, the gluconic acid crystals are condensed and crystallized to obtain gluconolactone, two times of evaporation and concentration are required, the evaporation energy consumption is high, meanwhile, acid is required for regeneration in the step of converting the ion exchange resin into the gluconic acid, water is used for washing, a large amount of acidic wastewater is generated, after alkali is used for neutralization, saline water containing excessive COD is generated, and the environmental pollution is caused and is difficult to treat.
Disclosure of Invention
Aiming at the defects of the conventional process for producing glucolactone, the invention aims to provide a production method of glucolactone, which is used for shortening a process route, reducing energy consumption and waste water discharge and reducing production cost.
The technical scheme adopted by the invention is as follows:
a clean production process of gluconolactone, 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 sequentially comprises microfiltration, ceramic membrane treatment or ultrafiltration treatment and chelating resin treatment;
(3) carrying out electrodialysis treatment on the feed liquid pretreated in the step (2) by using a bipolar membrane electrodialysis device with two compartments (an alkali liquid compartment/a feed liquid compartment) equipped with a bipolar membrane and a cation exchange membrane, and respectively obtaining a gluconic acid solution and a sodium hydroxide solution in the feed liquid compartment and the alkali liquid compartment, wherein the sodium hydroxide solution is used for adjusting the pH value of the fermentation system in the step (1);
(4) treating the gluconic acid solution obtained in the step (3) by using cation exchange resin to remove sodium ions;
(5) and (4) evaporating and crystallizing the gluconic acid solution treated in the step (4) to obtain the glucolactone.
In the step (1), glucose oxidase is adopted to oxidize glucose, hydrogen peroxide is generated in the process and has certain toxicity to the glucose oxidase, catalase is added to decompose the hydrogen peroxide into water and oxygen, so that the oxidation reaction is continued, and meanwhile, a sodium hydroxide solution with a certain concentration is slowly added to maintain the pH value of the environment and protect the activity of the enzyme. Preferably, the concentration of the glucose solution is 25 wt% to 60 wt%. Preferably, the concentrations of glucose oxidase and catalase in the fermentation system are 0.3-0.5 wt% and 0.2-0.5 wt%, respectively. Preferably, the fermentation is carried out for 20-40 hours at a temperature of 30-40 ℃ and a pH of the system of 3.5-4.5, so as to obtain a fermentation liquid. The glucose oxidase and catalase may be added in a batch manner.
In step (2) of the present invention, preferably, the pore size of the filter element of the microporous filter used for the microporous filtration is 1 to 5 μm.
In step (2) of the present invention, the ceramic membrane treatment or ultrafiltration treatment is performed to filter out protein substances in the solution. Preferably, the ceramic membrane treatment adopts a ceramic membrane with the thickness of 20-100nm, and the operating pressure is 0.1-0.4 MPa. Preferably, the ultrafiltration membrane used in the ultrafiltration treatment is a hollow fiber membrane or a roll-type ultrafiltration membrane, the cut-off molecular weight of the adopted ultrafiltration membrane is 1000-50000, the membrane has good pollution resistance and pollution blockage, and the operating pressure of the ultrafiltration treatment is 0.1-0.4 Mpa.
In step (2) of the present invention, the chelating resin treatment is performed for the purpose of removing polyvalent metal ions from the fermentation broth, so that it is preferable to use a polyvalent cation chelating resin such as: CH-93, LSC-500, etc., which are chelating resins for polyvalent cations (e.g., Ca)2+，Mg2+,Fe2+,Fe3+Etc.) strong adsorption capacity.
In step (3) of the present invention, the bipolar membrane electrodialysis device equipped with a bipolar membrane and a cation exchange membrane comprises a dc power supply, an anode plate connected to the positive electrode of the power supply, a cathode plate connected to the negative electrode of the dc power supply, and a membrane stack disposed between the anode plate and the cathode plate, wherein the membrane stack is formed by sequentially arranging and assembling bipolar membranes and cation exchange membranes at intervals, the outermost membrane is the bipolar membrane, two adjacent membranes are separated by a partition plate, one group of the bipolar membranes, the cation exchange membrane and the bipolar membrane constitute an electrodialysis unit of two compartments (an alkali solution compartment/a feed solution compartment), and at least one electrodialysis unit is provided in the membrane stack; an electrode 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 connected with a liquid tank and forms a loop through a circulating pump; the polar liquid chambers are respectively externally connected with polar liquid tanks and form a loop through a circulating pump.
The step (3) of the present invention is specifically performed as follows: introducing the pretreated fermentation liquor into a liquor chamber of the bipolar membrane electrodialysis device, introducing pure water into an alkali liquor chamber, introducing a sodium sulfate solution into an electrode liquor chamber, starting a circulating pump to fill the membrane stack with the liquor and circulate, starting a power supply to carry out electrodialysis treatment, generating sodium hydroxide in the alkali liquor chamber, and generating gluconic acid in the liquor chamber. The skilled person can screen the membranes and set the appropriate electrodialysis operating conditions as the case may be. Generally, the screening of the membranes of the electrodialysis unit is based on the resistance and current efficiency of the stack, preferably lower resistance and higher current efficiency, which means lower process costs; and the electrodialysis condition is determined according to the material liquid property and the membrane resistance, and corresponding voltage and current are selected within the limit current density. Preferably, the bipolar membrane is selected from bipolar membranes produced by fumtech in Germany, the cation exchange membrane is selected from cation exchange membranes produced by Techstan technologies GmbH, and the membrane stack consists of 50-200 groups of electrodialysis units. Preferably, the electrodialysis conditions are: controlling the current density of the DC electric field to be 100-600A/m2Controlling the temperature to be 5-40 ℃, when the liquid conductivity in the feed liquid chamber is reduced to 3-5 ms/cm and the pH is reduced to 2-2.3, stopping the operation, obtaining a mixed liquid of gluconic acid and sodium gluconate from the feed liquid chamber, wherein the conversion rate of the sodium gluconate reaches over 85-95%, the current efficiency reaches about 70%, and obtaining 6-10% of hydroxide in the alkali liquid chamberA sodium solution.
In step (4) of the present invention, the cation exchange resin is preferably a strong acid type 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 performed 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 to achieve the purpose of reducing production cost.
Drawings
FIG. 1 is a flow chart of the process for producing gluconolactone according to the invention;
FIG. 2 is a schematic diagram of a principle of producing gluconic acid by bipolar membrane electrodialysis;
FIG. 3 is a schematic flow diagram of the conversion of sodium gluconate by bipolar membrane electrodialysis.
Detailed description of the invention
The technical solution of the present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto:
the bipolar membrane electrodialysis device used in the embodiment of the invention is shown in schematic diagrams as 2 and 3, and comprises a direct current power supply, an anode plate connected with the positive electrode of the power supply, a cathode plate connected with the negative electrode 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 bipolar membranes and cation exchange membranes at intervals, the outermost membrane is the bipolar membrane, two adjacent membranes are separated by a partition plate, one group of the bipolar membranes, the cation exchange membranes and the bipolar membranes form an electrodialysis unit with two compartments (an alkali liquid compartment/a feed liquid compartment), and at least one electrodialysis unit is arranged in the membrane stack; an electrode 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 connected with a liquid tank and forms a loop through a circulating pump; the polar liquid chambers are respectively externally connected with polar liquid tanks and form a loop through a circulating pump.
Example 1
5t of a 50 wt.% glucose solution were slowly added to 10m3In the fermentation tank, 20kg of glucose oxidase and 15kg of catalase were slowly added into the fermentation tank at the same time, the added enzymes were from Tianjin Novist enzyme preparation company, 25% -32% sodium hydroxide solution was continuously added to adjust the pH value, the pH value was controlled at 5, and the temperature was controlled at 40 ℃. After 24h fermentation, pumping the fermentation liquor into a 5m container through a 1 micron microporous filter3And an ultrafiltration circulating water tank. The ultrafiltration equipment is a Chinese-style equipment, the selected membrane is a polysulfone hollow fiber membrane with the molecular weight cut-off of 5 ten thousand, the operating pressure is 0.3MPa, and the flux is 0.5m3The ultrafiltration recovery rate reaches 98 percent. The ultrafiltered permeate is pumped into a feed liquid chamber of a bipolar membrane electrodialysis system after passing through a chelate resin tank of CH-93 type, pure water is added into an alkali liquid chamber, a 3% sodium sulfate solution is added into an electrode liquid chamber, and a membrane stack of the bipolar membrane electrodialysis system is a two-compartment membrane stack (the effective area is 15m, the length is 800mm, the height is 800 mm) with the width being 400 x2) The membrane stack consists of 50 groups of electrodialysis units. The adopted bipolar membrane is a bipolar membrane imported from Fumatech of Germany, and the cation exchange membrane is selected from cation exchange membranes CTM-1 produced by Cylan film company. The circulation pump of each compartment is turned on, and the flow rate is controlled to be 3-5m3After 2min, the DC power supply is turned on, and the current density is controlled to be 300A/m2When the conductivity of the feed liquid is reduced to 5ms/cm and the pH value is 2.3, the reaction is stopped, the reaction is carried out for 8 hours, and the conversion rate of the sodium gluconate reaches 95.5 percent. And pumping the solution in the feed liquid chamber into a 001 x 7 strong acid type ion exchange resin tank, pumping into an MVR concentration crystallization tank, controlling the temperature at 60-80 ℃, and crystallizing for 48 hours to obtain 1.5t of product with the purity of more than 99%.
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 the example 1, and 1.55t of product with the purity of more than 99 percent is finally obtained.
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 steps are the same as example 1, and 1.5t of product with the purity of more than 99 percent is finally obtained.
Example 4
This example is substantially the same as example 1, and on this basis the ultrafiltration system employs a mesoporous ultrafiltration membrane with a molecular weight cut-off of 10000. The subsequent steps are the same as example 1, and 1.5t of product with the purity of more than 99 percent is finally obtained.
Example 5
The present embodiment is basically the same as embodiment 1, and on this basis, the membrane adopted by the ultrafiltration system is a roll-type ultrafiltration membrane, and the molecular weight cut-off is 30000. The subsequent steps are the same as example 1, and 1.54t of product with purity of more than 99% is finally obtained.
Example 6
The present embodiment is basically the same as embodiment 2, and on this basis, the membrane adopted by the ultrafiltration system is a roll type ultrafiltration membrane, and the molecular weight cut-off is 10000.
Example 7
30t of a 50% glucose solution were slowly added to 50m3In the fermentation tank, 120kg of glucose oxidase and 120kg of catalase were added simultaneously to the fermentation tank, and sodium hydroxide solution was continuously added to adjust the pH, the pH was controlled at 4.5, and the temperature was controlled at 40 ℃. After 24h fermentation, the fermentation liquor is pumped into an ultrafiltration circulating water tank after passing through a 1 micron microporous filter by a pump. The ultrafiltration equipment is 8040 industrialized equipment, the selected membrane is a roll-type ultrafiltration membrane with the molecular weight cutoff of 3 ten thousand, the operating pressure is 0.4MPa, the flux is 2m3/h, and the ultrafiltration recovery rate reaches 97.5 percent. The permeate of ultrafiltration is pumped into a feed liquid water tank of a bipolar membrane electrodialysis system after passing through a chelate resin tank of CH-93 type, pure water is added into an alkali chamber, a 3% sodium sulfate solution is added into an electrode liquid chamber, and the membrane stack of the bipolar membrane electrodialysis system is a two-compartment membrane stack (the effective area is 25 m) with the membrane stack of 500 x 1100mm x 4002). The membrane stack consisted of 50 electrodialysis units. The adopted bipolar membrane is a bipolar membrane imported from Fumatech of Germany, and the cation exchange membrane is selected from cation exchange membranes CTM-1 produced by Cylan film company. Circulating pumps of each compartmentThe flow rate is controlled to be 3-5m3After 2min, the DC power supply is turned on, and the current density is controlled to be 300A/m2When the conductivity of the feed liquid is reduced to 3ms/cm and the pH value is 2, the reaction is stopped, the reaction is carried out for 20 hours, and the conversion rate of the sodium gluconate reaches 95.2 percent. Pumping the solution in the feed liquid chamber into a 001 x 7 strong acid type ion exchange resin tank, pumping into an MVR concentration crystallization tank, controlling the temperature at 60-80 ℃, and crystallizing for 48 hours to obtain 10t of product with purity>99％。
Using example 1 of the present invention as an example, the energy consumption and cost for producing one ton of gluconolactone was compared with the conventional process, and the results are shown in the following table:
TABLE 1
| Name (R) | Conventional process | The process |
| Ton energy consumption cost | 1000 Yuan | 750 yuan |
| Ton waste water | 13 ton of | 1 ton of |
| Ton cost | 6300 yuan | 5200 |
Therefore, the clean production process can reduce the energy consumption cost by more than 20%, simultaneously reduce the wastewater discharge by more than 90%, reduce the production cost by more than 15%, and has remarkable progress.
Claims (10)
1. A production method of gluconolactone, 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 sequentially comprises microfiltration, ceramic membrane treatment or ultrafiltration treatment and chelating resin treatment;
(3) carrying out electrodialysis treatment on the feed liquid pretreated 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 liquor chamber, wherein the sodium hydroxide solution is used for adjusting the pH value of the fermentation system in the step (1);
(4) treating the gluconic acid solution obtained in the step (3) by using cation exchange resin to remove sodium ions;
(5) and (4) evaporating and crystallizing the gluconic acid solution treated in the step (4) to obtain the glucolactone.
2. The method for producing gluconolactone according to claim 1, wherein: in the step (1), the concentration of the glucose solution is 25-60 wt%, the concentrations of the glucose oxidase and the catalase in the fermentation system are respectively 0.3-0.5 wt% and 0.2-0.5 wt%, the pH of the system is controlled between 3.5-4.5, and the fermentation is carried out at 30-40 ℃ for 20-40 hours, so as to obtain the fermentation liquor.
3. The method for producing gluconolactone according to claim 1, wherein: in the step (2), the filter element aperture of the microporous filter adopted by the microporous filtration is 1-5 μm.
4. The method for producing gluconolactone 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 0.1-0.4 MPa.
5. The method for producing gluconolactone according to claim 1, wherein: the ultrafiltration membrane adopted in the ultrafiltration treatment is a hollow fiber membrane or a roll-type ultrafiltration membrane, the molecular weight cut-off of the adopted ultrafiltration membrane is 1000-50000, and the operating pressure of the ultrafiltration treatment is 0.1-0.4 Mpa.
6. The method for producing gluconolactone according to claim 1, wherein: in the step (2), the chelating resin treatment uses a polyvalent cation chelating resin.
7. The method for producing gluconolactone according to claim 1, wherein: in the step (2), the polyvalent cation chelating resin is CH-93 or LSC-500.
8. The method for producing gluconolactone according to claim 1, wherein: the step (3) is specifically implemented as follows: introducing the pretreated fermentation liquor into a liquor chamber of the bipolar membrane electrodialysis device, introducing pure water into an alkali liquor chamber, introducing a sodium sulfate solution into an electrode liquor chamber, starting a circulating pump to fill the membrane stack with the liquor and circulate, starting a power supply to carry out electrodialysis treatment, generating sodium hydroxide in the alkali liquor chamber, and generating gluconic acid in the liquor chamber.
9. The method for producing gluconolactone according to claim 1, wherein: in the step (3), a 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 DC electric field to be 100-600A/m2And controlling the temperature to be 5-40 ℃, and stopping operation when the conductivity of the liquid in the feed liquid chamber is reduced to 3-5 ms/cm and the pH is reduced to 2-2.3.
10. The method for producing gluconolactone 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111778294A (en) * | 2020-07-20 | 2020-10-16 | 山东欣宏药业有限公司 | Method for preparing gluconic acid and method for preparing zinc gluconate by using gluconic acid |
| CN114452821A (en) * | 2022-01-26 | 2022-05-10 | 中国科学技术大学 | Bipolar membrane electrodialysis device, method for preparing regenerated alkali by using bipolar membrane electrodialysis device and application of bipolar membrane electrodialysis device |
| CN115448900A (en) * | 2021-06-09 | 2022-12-09 | 安徽省兴宙医药食品有限公司 | Production process of gluconic acid-delta-lactone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321688A (en) * | 2011-06-20 | 2012-01-18 | 华东理工大学 | Method for separating glucose |
| US20130245320A1 (en) * | 2010-08-19 | 2013-09-19 | Companhia Refinadora Da Amazonia | Method for obtaining lactic acid with a high degree of purity from fermentative liquor |
| CN104328452A (en) * | 2014-07-22 | 2015-02-04 | 宜宾丝丽雅集团有限公司 | Production process of gluconic acid by bipolar membrane electrodialysis method |
| CN204151425U (en) * | 2014-07-22 | 2015-02-11 | 宜宾丝丽雅集团有限公司 | Production system of gluconic acid by bipolar membrane electrodialysis method |
-
2019
- 2019-12-31 CN CN201911414114.XA patent/CN111172205B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130245320A1 (en) * | 2010-08-19 | 2013-09-19 | Companhia Refinadora Da Amazonia | Method for obtaining lactic acid with a high degree of purity from fermentative liquor |
| CN102321688A (en) * | 2011-06-20 | 2012-01-18 | 华东理工大学 | Method for separating glucose |
| CN104328452A (en) * | 2014-07-22 | 2015-02-04 | 宜宾丝丽雅集团有限公司 | Production process of gluconic acid by bipolar membrane electrodialysis method |
| CN204151425U (en) * | 2014-07-22 | 2015-02-11 | 宜宾丝丽雅集团有限公司 | Production system of gluconic acid by bipolar membrane electrodialysis method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111778294A (en) * | 2020-07-20 | 2020-10-16 | 山东欣宏药业有限公司 | Method for preparing gluconic acid and method for preparing zinc gluconate by using gluconic acid |
| CN115448900A (en) * | 2021-06-09 | 2022-12-09 | 安徽省兴宙医药食品有限公司 | Production process of gluconic acid-delta-lactone |
| CN114452821A (en) * | 2022-01-26 | 2022-05-10 | 中国科学技术大学 | Bipolar membrane electrodialysis device, method for preparing regenerated alkali by using bipolar membrane electrodialysis device and application of bipolar membrane electrodialysis device |
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