CN113402380A - Method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid - Google Patents
Method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid Download PDFInfo
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- CN113402380A CN113402380A CN202110738191.1A CN202110738191A CN113402380A CN 113402380 A CN113402380 A CN 113402380A CN 202110738191 A CN202110738191 A CN 202110738191A CN 113402380 A CN113402380 A CN 113402380A
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- China
- Prior art keywords
- calcium gluconate
- waste liquid
- solution
- crystallization
- magnesium chloride
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- 239000004227 calcium gluconate Substances 0.000 title claims abstract description 58
- 229960004494 calcium gluconate Drugs 0.000 title claims abstract description 58
- 235000013927 calcium gluconate Nutrition 0.000 title claims abstract description 58
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 title claims abstract description 58
- 239000007788 liquid Substances 0.000 title claims abstract description 53
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002425 crystallisation Methods 0.000 title claims abstract description 26
- 230000008025 crystallization Effects 0.000 title claims abstract description 26
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000005086 pumping Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000003306 harvesting Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004040 coloring Methods 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000000855 fermentation Methods 0.000 description 6
- 230000004151 fermentation Effects 0.000 description 6
- 241000228245 Aspergillus niger Species 0.000 description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 239000000174 gluconic acid Substances 0.000 description 3
- 235000012208 gluconic acid Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- 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 description 1
- CZNVSLGYWMSMKE-OPDGVEILSA-K Ferric gluconate Chemical compound [Fe+3].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O CZNVSLGYWMSMKE-OPDGVEILSA-K 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960005069 calcium Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229940069978 calcium supplement Drugs 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid, which comprises the following operation steps; the first step is as follows: filtering impurities in the mixed solution, collecting the waste liquid in a centralized way, transferring and storing the waste liquid by adopting a collecting box, installing a water pump to suck and pump the waste liquid, arranging a filter box, installing a micron filter membrane in an inlet of the filter box, and pumping the waste liquid to the filter membrane by adopting the water pump to filter fine impurities in the waste liquid. According to the invention, the filtration with different effects is carried out twice by adopting the 0.45-micron filter membrane, so that the impurities in the waste liquid are effectively cleaned, the crystal acquisition purity is improved in the subsequent acquisition, the coloring separation is realized by matching with the cold water sleeve, the separation of high-capacity calcium gluconate crystals is improved, the preparation efficiency is improved, the atomized magnesium chloride neutral salt is added for easy cleaning when the calcium gluconate is acquired, the purity of the calcium gluconate crystals is improved, and the preparation method is good.
Description
Technical Field
The invention relates to the technical field of calcium gluconate purification, in particular to a method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid.
Background
Calcium gluconate (calcium gluconate) is calcium salt of gluconic acid, has molecular formula of C12H22CaO 14. H2O, molecular weight of 448.40, melting point of 201 deg.C, is white crystal or powder, odorless and tasteless, and is soluble in cold water, easily soluble in hot water, and insoluble in anhydrous ethanol, chloroform or diethyl ether. The calcium gluconate is an important organic calcium, is clinically used as a calcium supplement, is a raw material for producing other gluconate (zinc gluconate, ferric gluconate and the like) and gluconic acid delta-lactone, and is an important chemical export product in China.
The method for preparing the calcium gluconate mainly comprises a chemical method and a fermentation method, wherein the fermentation method comprises the following process flows:
(1) saccharification: starch, rice, flour or corn flour are used as raw materials, and various amylases are added for saccharification after heating and curing to generate glucose.
(2) Fermenting aspergillus niger: inoculating Aspergillus niger to the saccharified liquid, oxidizing glucose into gluconic acid by the Aspergillus niger, and continuously pumping CaCO3 slurry to neutralize acid in the fermentation liquid to continue fermentation, so that the gluconic acid in the fermentation liquid is converted into calcium gluconate.
(3) Extracting calcium gluconate: after the fermentation is finished, impurities such as thalli and the like are filtered, and the filtrate contains calcium gluconate. The filtrate was concentrated to saturation at 100 ℃ and contained about 200g/L calcium gluconate. After cooling to 20 ℃, standing for 24h to allow crystals to naturally separate out or adding seed crystals to promote crystal formation. The crystals were washed with a small amount of ethanol and then dried at 80 ℃ under reduced pressure to give the final product.
After the existing calcium gluconate crystallization waste liquid is processed, produced and formed, special treatment is not usually carried out, more impurity impurities and calcium gluconate are remained in the waste liquid, the calcium gluconate acquisition amount is reduced along with discharge treatment, the waste liquid is rich in impurities and is mixed with part of calcium gluconate to pollute the environment along with discharge, the waste water treatment quality is insufficient, the treatment effect is poor, and an effective mode for further extracting the calcium gluconate is lacked.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid, and solves the problems mentioned in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid comprises the following operation steps;
the first step is as follows: filtering impurities in the mixed solution
The waste liquid is collected in a centralized manner, the waste liquid is transferred and stored by adopting a collecting box, a water pump is arranged to pump the waste liquid out, a filter box is arranged, a filter membrane with the thickness of 0.45 mu m is arranged in an inlet of the filter box, the waste liquid is pumped to the filter membrane by adopting the water pump, so that fine impurities in the waste liquid are filtered, and calcium gluconate dissolved in the waste liquid passes through and is mixed in a filtered solution.
The second step is that: heating and concentrating the filtered solution
The filtered solution is intensively recycled into the heating box, magnesium chloride powder is added into the heating box, magnesium chloride is gradually heated by adopting a mixing and stirring mode, the heating temperature is increased, the solution is uniformly stirred while being heated, the content of the solution in the heating box is reduced to three fifths of the original solution, the stirring is stopped, the cover is closed, the sealing is carried out, and the heated solution is kept stand and cooled.
The third step: crystallization out
And (3) easily placing the concentrated solution in a crystallization barrel, adding ethanol into the concentrated solution, placing the crystallization barrel in a cold water sleeve after adding the ethanol, keeping cold water to infiltrate four sides of the crystallization barrel, reducing the temperature of the mixed solution, reducing the mixing speed of the ethanol, and enabling the clean barrel to be crystallized and separated out along with the time.
The fourth step: calcium gluconate harvest
Upwards placing a filter membrane with the diameter of 0.45 mu m on the top of a liquid outlet, pouring the supernatant liquid, enabling the separated clear liquid to flow out through the filter membrane with the diameter of 0.45 mu m, enabling the calcium gluconate crystals to be filtered and remained, cleaning the filtered crystals through spraying of a magnesium chloride solution, and then drying and purifying at the temperature of 70 ℃ to obtain the calcium gluconate.
Preferably, the content of magnesium chloride in the second step is the content of magnesium chloride in each heating box, and is 70 g.
Preferably, the stirring manner in the second step is rotating in the same direction, and the heating temperature is 100 ℃.
Preferably, the cooling time in the second step is 5-6 hours, and the ambient temperature is kept at 20-25 ℃.
Preferably, the temperature of the cold water in the third step is 0-5 ℃, and the cold water is placed in the cold water for 5-6 hours.
Preferably, the atomized magnesium chloride solution is adopted for spraying in the fourth step, and the spraying times of the surface of the precipitated crystal are specifically ensured to be 4-5 times, wherein the temperature of the magnesium chloride solution is 50-55 ℃.
The beneficial effects are as follows:
according to the invention, the filtration with different effects is carried out twice by adopting the 0.45-micron filter membrane, so that the impurities in the waste liquid are effectively cleaned, the crystal acquisition purity is improved in the subsequent acquisition, the coloring separation is realized by matching with the cold water sleeve, the separation of high-capacity calcium gluconate crystals is improved, the preparation efficiency is improved, the atomized magnesium chloride neutral salt is added for easy cleaning when the calcium gluconate is acquired, the purity of the calcium gluconate crystals is improved, and the preparation method is good.
Detailed Description
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: a method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid comprises the following operation steps;
the first step is as follows: filtering impurities in the mixed solution
The waste liquid is collected in a centralized manner, the waste liquid is transferred and stored by adopting a collecting box, a water pump is arranged to pump the waste liquid out, a filter box is arranged, a filter membrane with the thickness of 0.45 mu m is arranged in an inlet of the filter box, the waste liquid is pumped to the filter membrane by adopting the water pump, so that fine impurities in the waste liquid are filtered, and calcium gluconate dissolved in the waste liquid passes through and is mixed in a filtered solution.
The second step is that: heating and concentrating the filtered solution
The filtered solution is intensively recycled into the heating box, magnesium chloride powder is added into the heating box, magnesium chloride is gradually heated by adopting a mixing and stirring mode, the heating temperature is increased, the solution is uniformly stirred while being heated, the content of the solution in the heating box is reduced to three fifths of the original solution, the stirring is stopped, the cover is closed, the sealing is carried out, and the heated solution is kept stand and cooled.
The third step: crystallization out
And (3) easily placing the concentrated solution in a crystallization barrel, adding ethanol into the concentrated solution, placing the crystallization barrel in a cold water sleeve after adding the ethanol, keeping cold water to infiltrate four sides of the crystallization barrel, reducing the temperature of the mixed solution, reducing the mixing speed of the ethanol, and enabling the clean barrel to be crystallized and separated out along with the time.
The fourth step: calcium gluconate harvest
Upwards placing a filter membrane with the diameter of 0.45 mu m on the top of a liquid outlet, pouring the supernatant liquid, enabling the separated clear liquid to flow out through the filter membrane with the diameter of 0.45 mu m, enabling the calcium gluconate crystals to be filtered and remained, cleaning the filtered crystals through spraying of a magnesium chloride solution, and then drying and purifying at the temperature of 70 ℃ to obtain the calcium gluconate.
Wherein, the content of the magnesium chloride in the second step is the content of the magnesium chloride in each heating box, and is specifically 70 g.
Wherein, the stirring mode in the second step is that the stirring device rotates in the same direction, and the heating temperature is 100 ℃.
Wherein the cooling time in the second step is 5-6 hours, and the ambient temperature is kept at 20-25 ℃.
Wherein the temperature of the cold water in the third step is 0-5 ℃, and the cold water is placed in the cold water for 5-6 hours.
Wherein, the atomized magnesium chloride solution is adopted for spraying in the fourth step, the spraying times of the surface of the precipitated crystal are particularly ensured to be 4-5 times, and the temperature of the magnesium chloride solution is 50-55 ℃.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid is characterized by comprising the following steps: comprises the following steps of;
the first step is as follows: filtering impurities in the mixed solution
Collecting the waste liquid in a centralized manner, transferring and storing the waste liquid by using a collecting box, installing a water pump to suck and pump the waste liquid out, arranging a filter box, installing a 0.45-micrometer filter membrane in an inlet of the filter box, pumping the waste liquid to the filter membrane by using the water pump, filtering fine impurities in the waste liquid, and allowing calcium gluconate dissolved in the waste liquid to pass through and be mixed in a filtered solution;
the second step is that: heating and concentrating the filtered solution
The filtered solution is intensively recycled into a heating box, magnesium chloride powder is added into the heating box, magnesium chloride is gradually heated in a mixing and stirring mode, the heating temperature is increased, the heating solution is uniformly stirred while being heated, the content of the solution in the heating box is reduced to three fifths of the content of the original solution, stirring is stopped, a cover is closed, sealing is carried out, and the heated solution is kept stand and cooled;
the third step: crystallization out
Placing the concentrated solution in a crystallization barrel easily, adding ethanol into the concentrated solution, placing the crystallization barrel in a cold water sleeve after adding the ethanol, keeping cold water to infiltrate four sides of the crystallization barrel, reducing the temperature of the mixed solution, reducing the mixing speed of the ethanol, and enabling the clean barrel to be crystallized and separated out along with the time;
the fourth step: calcium gluconate harvest
Upwards placing a filter membrane with the diameter of 0.45 mu m on the top of a liquid outlet, pouring the supernatant liquid, enabling the separated clear liquid to flow out through the filter membrane with the diameter of 0.45 mu m, enabling the calcium gluconate crystals to be filtered and remained, cleaning the filtered crystals through spraying of a magnesium chloride solution, and then drying and purifying at the temperature of 70 ℃ to obtain the calcium gluconate.
2. The method for further extracting calcium gluconate from the waste liquid after calcium gluconate crystallization according to claim 1, wherein the method comprises the following steps: and in the second step, the content of magnesium chloride is the content of magnesium chloride in each heating box, and is specifically 70 g.
3. The method for further extracting calcium gluconate from the waste liquid after calcium gluconate crystallization according to claim 1, wherein the method comprises the following steps: and the stirring mode in the second step is that the stirring device rotates in the same direction, and the heating temperature is 100 ℃.
4. The method for further extracting calcium gluconate from the waste liquid after calcium gluconate crystallization according to claim 1, wherein the method comprises the following steps: and the cooling time in the second step is 5-6 hours, and the ambient temperature is kept at 20-25 ℃.
5. The method for further extracting calcium gluconate from the waste liquid after calcium gluconate crystallization according to claim 1, wherein the method comprises the following steps: the temperature of the cold water in the third step is 0-5 ℃, and the cold water is placed in the cold water for 5-6 hours.
6. The method for further extracting calcium gluconate from the waste liquid after calcium gluconate crystallization according to claim 1, wherein the method comprises the following steps: and in the fourth step, atomized magnesium chloride solution is adopted for spraying, and the spraying times of the surface of the precipitated crystal are specifically ensured to be 4-5 times, wherein the temperature of the magnesium chloride solution is 50-55 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110738191.1A CN113402380A (en) | 2021-06-30 | 2021-06-30 | Method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110738191.1A CN113402380A (en) | 2021-06-30 | 2021-06-30 | Method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid |
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| CN113402380A true CN113402380A (en) | 2021-09-17 |
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| CN202110738191.1A Pending CN113402380A (en) | 2021-06-30 | 2021-06-30 | Method for further extracting calcium gluconate from calcium gluconate crystallization waste liquid |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016239A (en) * | 2007-03-06 | 2007-08-15 | 韦传宝 | Method of extracting calcium gluconate from mother liquid after calcium gluconate crystallization |
| CN101736043A (en) * | 2010-01-25 | 2010-06-16 | 浙江天益食品添加剂有限公司 | Method for producing calcium gluconate by fermenting Aspergillus niger |
| CN106008196A (en) * | 2016-05-27 | 2016-10-12 | 韦彩勇 | Purifying method for calcium gluconate solution |
| CN110452111A (en) * | 2019-08-21 | 2019-11-15 | 山东齐都药业有限公司 | A kind of method for crystallising of calcium gluconate |
-
2021
- 2021-06-30 CN CN202110738191.1A patent/CN113402380A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016239A (en) * | 2007-03-06 | 2007-08-15 | 韦传宝 | Method of extracting calcium gluconate from mother liquid after calcium gluconate crystallization |
| CN101736043A (en) * | 2010-01-25 | 2010-06-16 | 浙江天益食品添加剂有限公司 | Method for producing calcium gluconate by fermenting Aspergillus niger |
| CN106008196A (en) * | 2016-05-27 | 2016-10-12 | 韦彩勇 | Purifying method for calcium gluconate solution |
| CN110452111A (en) * | 2019-08-21 | 2019-11-15 | 山东齐都药业有限公司 | A kind of method for crystallising of calcium gluconate |
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