CN101182062A - Method for treating waste water containing sericin protein - Google Patents
Method for treating waste water containing sericin protein Download PDFInfo
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- CN101182062A CN101182062A CNA2007100930918A CN200710093091A CN101182062A CN 101182062 A CN101182062 A CN 101182062A CN A2007100930918 A CNA2007100930918 A CN A2007100930918A CN 200710093091 A CN200710093091 A CN 200710093091A CN 101182062 A CN101182062 A CN 101182062A
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Abstract
The invention discloses a sericin protein containing wastewater processing method, which uses the coordination reaction between sericin and metal to synthesize a sericin protein-metal complex. The complex is used as a flocculant to coagulate and settle sericin in wastewater of silk mills to effectively treat the wastewater. At last, sericin proteins are recovered with low cost through a dilute acid washing method. The method solves environmental pollution problems caused by the high chemical oxygen demand of the wastewater, effectively protects the water quality, recovers the sericin in the wastewater with low cost and changes wastes into valuables. The development and the implementation of the new process will bring both good social benefits and considerable economic benefits for silk enterprises in the wastewater treatment. Therefore, the invention is provided with a wide industrial application prospect.
Description
Technical field
The present invention relates to a kind of method of wastewater treatment, specifically refer to a kind of treatment process of waste water containing sericin protein, present method can be carried out efficient recovery cheaply to the silk gum in the waste water again when administering Silk Mill's sewage.
Background technology
The waste water that processing industries such as silk enterprise wastewater and starch, beer, fruit juice produce is very different, and its essential substance is the silk gum and the pupal acid of stripping.Since the thirties in 20th century; China; Japan; the scientists of Korea S is just to the structure of silk; character etc. have been carried out a large amount of research; in result up to now; the fiber utilization of having recognized silk partly is fibroin; and the big processable globular proteins of surface viscosity---the main effect of silk gum is to have played in silk reeling process silk is dissociated smoothly; the effect of protection fibroin; and last squeeze is not contain silk gum; the overwhelming majority of silk gum is in cocoon cooking; be discharged with factory effluent in the production processes such as filature, remaining part is also thoroughly removed in refining.Therefore, Silk Mill's waste water main component is the sericine of high density, and the waste water protein of these high densitys, flows into behind the river course dissolved oxygen in the consume water in large quantities, causes the water quality oxygen enrichmentization, destroys original water quality, causes environmental pollution.On the other hand, silk gum itself also is a kind of important protein matter resource, is made up of 18 seed amino acids, can be used for the back arrangement of health textile etc.Rise along with biomaterial, degradable silk gum has demonstrated the better application prospect than fibroin etc., now be utilized as cosmetics additive, foodstuff additive, medicine, biomaterial, functional materials etc., its price has also reached about 100,000 U.S. dollar/tons in the international market, and the utilization again of silk gum also becomes the competition spot of each enterprise.Extract silk gum, turn waste into wealth, imperative.These silk gum that are lost of silk enterprise, not having can efficient recovery, has also caused great resource waste.Adopt reasonable method and technology, the sericin that extracts in the waste water is fully utilized, and not only can preserve the ecological environment but also can obtain higher economic benefit, is the new problem to proposing in the silk scale wastewater treatment in recent years.
And in recent years both at home and abroad to the processing of silk gum waste water and to carry out the research that silk gum reclaims in the waste water simultaneously also many.Korea S has some to extract the patent of the method for sericin from the real silk scouring waste, it mainly is that the pH value of scouring waste is regulated, the temperature adjustment degree adds polymeric flocculant more again, and sericin is settled down, with 3000-5000rpm rotating speed centrifugation 10 minutes, or obtain sericin with molecular sieve filtration, this method is comparatively complicated, the polymeric flocculant of use be difficult to remove after silk gum combines, the cost height easily forms secondary pollution.China Donghua University adopts neutral polysulfone hollow fibre tubular type ultra-filtration equipment, and the cocoon cooking water in Silk Mill's waste water is studied in the ultrafiltration under the different pH condition, and this method exists cost too high, can't be applied to the shortcoming of actual production soon.Institutes Of Technology Of Zhejiang etc. have also adopted the adding medicine precipitation method that refilters that concentration maximum in Silk Mill's waste water and easily corrupt rotten frigon waste water have been carried out the one-level processing.Also have Zhejiang Environmental Protection Research Academy to adopt anaerobism-A/O contact oxidation technology to handle Silk Mill's waste water, obtained certain achievement.But these researchs all mainly concentrate on the waste water treatment aspect, and are all not mentioned for extracting the sericin powder therein, have the secondary pollution problem.Even if filtered out sericine, also owing to the sericine that filters out has taken place to engage with the medicine as flocculation agent that adds in addition, add this throw out water content height that contains silk gum, have viscosity and contain impurity such as the various residues (as by well-done pupal cell micro mist etc.) that produce in ash content, fat, waxy substance, the silk reeling process, its purification technique becomes a big difficult point.Still there is the problem of secondary treatment in the mud that is contained composition such as sericin by depleted once more.It simultaneously also is significant wastage to the natural polymer child resource.Consider from the angle of environmental protection and benefit, administer Silk Mill's sewage, simultaneously silk gum being reclaimed will be an inevitable trend.
Summary of the invention
At the prior art above shortcomings, the purpose of this invention is to provide a kind of treatment process that when administering Silk Mill's waste water, can carry out the waste water containing sericin protein of low-cost efficient recovery again to the sericin in the waste water.
The object of the present invention is achieved like this:
The treatment process of waste water containing sericin protein is characterized in that: it comprises the steps:
1. at first prepare the sericin metal complex;
2. the sericin metal complex that makes is added as flocculation agent and contain in the waste water of sericin, the add-on of sericin metal complex is 2～10 milligrams in every milliliter of waste water, the above-mentioned container that waste water and flocculation agent are housed is put into the constant temperature water bath shaking table, water temperature remains on about 25～35 ℃, make its oscillatory reaction 6～10 hours, extract throw out;
3. in the throw out that obtains, add weak acid scrubbing, with magnetic stirrer after 1～12 hour centrifugal gained drying precipitate be sericin powder.
The sericin metal complex of described the first step preparation is a transition metal complex, and transition metal is meant the metal of those perpendicular row of iron in the periodic table of elements, cobalt, nickel, zinc and copper place.The preparation method of transition metal complex was two steps: 1, obtain sericin purification solution-use soxhlet extraction device earlier, with ether the cocoon shell is carried out 24～48 hours cycling extractions or immersion treatment to remove waxy substance wherein, boil with ethanol again after the distilled water wash drying and removed carbohydrate and ash content in 0.5～1.5 hour, clean dry, in pure water, boiled again 2～4 hours, remove fiber, remaining thick liquid is silk gum solution, is that the thick back of 5～7mg/ml is stand-by with the sericin solution concentration that obtains to its concentration; 2, the preparation of sericin metal complex-adding metal chlorate solution (or solution of metal sulfates) and KCl solution in the above-mentioned sericin purification solution that obtains, its add-on is: add the metal chlorate solution 3.25ml of 0.25mol/L and the KCl solution 3.25ml of 2.5mol/L in every 100ml sericin purification solution, with concentration is the KOH solution adjusting pH value of 0.05mol/L, add KOH solution while stirring, make PH＞9.1, make coordination reach balance with magnetic stirrer, it is standby that filtration obtains metal complex.
Described metal chlorate is FeCl
3, ZnCl
2, CoCl
2Or CuCl
2
Described diluted acid is dilute hydrochloric acid or dilute sulphuric acid, and its concentration is 0.001mol/ml, and the add-on of diluted acid is 1.5～3.0 milliliters in every milliliter of throw out.
The present invention has initiated a kind of novel process of handling the silk enterprise wastewater through the silk gum of metal complex reaction itself of using, and it has the beneficial effect of following two aspects at least: one, can effectively administer the waste water of Silk Mill's discharging.Experiment shows, greatly reduces by the sericine content in present method processed waste water, and the highest range of decrease can reach 59%, and the chemical oxygen demand (COD) of waste water also correspondingly greatly reduces before and after handling, and has protected original water quality effectively, has avoided environmental pollution; Two, realized the silk gum in the waste water is carried out low-cost efficient recovery.Owing to adopt silk gum albumen metal complex the silk gum in the waste water to be precipitated as flocculation agent, so the silk gum dilute acid wash of post precipitation just can be at an easy rate except that taking off metal ion in the flocculation agent and other impurity in the silk gum, gained silk gum purity height, cost is low, is easy to industrial application; Three, present method is when administering waste water, and the sedimentation time after flocculation agent adds is shorter than traditional flocculation agent sedimentation time, can enhance productivity significantly thus.
Exploitation of this novel process and enforcement will also bring comparatively considerable economic for silk enterprise when good social effect is brought in the wastewater treatment aspect, therefore have wide prospect in industrial application.
Embodiment
Introduce the present invention in detail below in conjunction with embodiment.
Core of the present invention is the silk gum (being the sericin metal complex) of metal complex reaction itself as in the pending Silk Mill's waste water of flocculation agent adding, makes the silk gum coagulative precipitation in the waste water and removed.Because metal is heavier, metal complexation has also changed electric field around the sericin simultaneously, thus can rapid precipitation, the time lacks, and the processing efficiency height is particularly suitable for industrial application.Simultaneously in follow-up silk gum removal process, because flocculation agent is the sericin metal complex, only needs be removed metal ion wherein and get final product, and the removal of metal ion itself is to be relatively easy to, therefore can reduce cost recovery greatly, and improve organic efficiency.
The concrete steps of present method are:
One, the preparation of sericin transition metal complex
This step not only will prepare metal complex, and metal ion is many as best one can in the metal complex, and amount of metal ion is many more, when wastewater treatment and the binding capacity of silk gum big more, the silk gum precipitation capacity is big more in the waste water, and treatment effect is just good more, and the sericin amount that subsequent recovery obtains is just many more.
This step is divided two little steps: 1, prepare the sericin purification solution earlier: use the soxhlet extraction device, with ether 12g cocoon shell is carried out about 24～48 hours cycling extractions or immersion treatment (actual adopt 24 hours cycling extractions) to remove waxy substance wherein, boil carbohydrate and the ash content of removing in 0.5～1.5 hour wherein with ethanol again after the distilled water wash drying, clean dry, in the 1000ml pure water, boiled 2～4 hours again, remove fiber, remaining thick liquid is silk gum solution.The fiber of removing is a fibroin fiber, is weighed as 10.07g after the drying, i.e. the about 1.93g of content of silk gum.It is stand-by that the sericin solution that obtains is concentrated to the thick back of about 100ml with rotatory evaporator, and recording its concentration is 6mg/ml.Silk gum yield about 18%.
2, preparation metal complex.Embodiment prepares metal complex respectively with two kinds of metal chlorates:
(1) iron(ic) chloride sericin metal complex preparation: the FeCl that in the 100ml beaker, injects sericin purification solution 80ml, 0.25mol/L
3The KOH solution of solution 2.6ml, 2.5mol/L KCl solution 2.6ml, usefulness 0.05mol/L is regulated pH value, adds alkali lye while stirring, and notes the variation of pH value.Make PH＞9.1, survey to such an extent that PH is 9.3.With magnetic stirrer 12 hours, make coordination reach balance, filter that to obtain metal complex standby.
(2) zinc chloride sericin metal complex preparation: the ZnCl that in the 100ml beaker, injects sericin purification solution 80ml, 0.25mol/L
2The KOH solution of solution 2.6ml, 2.5mol/L KCl solution 2.6ml, usefulness 0.05mol/L is regulated pH value, makes PH＞9.1.With magnetic stirrer 12 hours, make coordination reach balance, filter that to obtain metal complex standby.
Except that KOH solution, above-mentioned alkaline solution also can be a NaOH solution.
Other metal chlorates are (as CoCl
2And CuCl
2) and metal sulfate (as ZnSO
4And CuSO
4Deng) method for preparing metal complex is the same.
Two, add waste water that silk mill is got in the test tube, as in the flocculation agent adding waste water, the add-on of sericin metal complex is 2～10 milligrams in every milliliter of waste water with the above-mentioned silk gum albumen metal Fe complex compound that makes or Zn complex compound.The above-mentioned test tube that waste water and flocculation agent are housed is put into the constant temperature water bath shaking table, and water temperature remains on about 25～35 ℃, makes its oscillatory reaction 6～10 hours, and it is standby to extract throw out with centrifuging.The waste water of this moment is the waste water after the processing, and content of silk gum wherein significantly reduces.
Three, (selecting concentration in the present embodiment for use is the dilute hydrochloric acid of 0.001mol/ml to add an amount of weak acid scrubbing in the throw out that second step is obtained, add 1.5～3 milliliters of dilute hydrochloric acid in every milliliter of throw out, certainly, dilute hydrochloric acid also can replace with dilute sulphuric acid), with magnetic stirrer after 1～12 hour the centrifuging and taking drying precipitate promptly obtain having removed the sericin powder of metal ion and part pupal acid, carbohydrate, other impurity.
The contrast experiment
Get same silk waste water and be divided into equal seven parts, every part of 5ml.Protein content is 8.450mg/ml in the preceding waste water of measurement processing earlier.Add silk gum albumen metal Fe complex compound in three parts of waste water therein again and handle as flocculation agent, its addition is respectively 10mg, 20mg and 30mg; Also having three parts flocculation agent is sericine, and its addition is similarly 10mg, 20mg and 30mg; Last portion does not add any flocculation agent and distinguishes in contrast.Wastewater treatment finishes, and gets each 1ml of supernatant liquor for every part and utilizes biuret method to measure processing back protein concn, and the difference of its protein concn is as shown in table 1.Table 1 data show, the sericin metal complex as flocculation agent can the coagulative precipitation wastewater from silk reeling in most sericine, reduced Protein content in the waste water, maximum has decreased by 59%, has reached the purpose that purifies water.According to the difference that adds the sericin metal complex, find by the contrast experiment, through the waste water after the processing of sericin ferrous metal complex compound, Protein content illustrates that than the 1.0～1.8mg/ml that lacked that handles with sericin sericin its flocculation ability after carrying out complex reaction with metal is greatly improved in its supernatant liquor.Sericine itself is owing to peptide bond reaction between protein, hydrogen bond action etc. also have proteinic effect in the flocculation waste water, but it is when staticly settling, need 48～72 hours ability all to precipitate approximately, and sericin metallic iron complex compound leaves standstill the back and only needs 12 hours just whole precipitations, and this is because after metal ion and the sericin generation complex reaction, changed sericin electric field on every side, make it be easy to coagulative precipitation, and metal ion is heavier relatively, easier deposition is got off.And just can sedimentary characteristic just be fit to the requirement of large-scale waste water treatment production line within a short period of time.Experiment shows that these two kinds of flocculation materials are directly proportional with its content in waste water to proteinic precipitation ability in the waste water.
The variation (mensuration of chemical oxygen demand adopt potassium dichromate process) of chemical oxygen demand of waste water before and after handling measured in experiment simultaneously, sees Table 2.As can be seen from Table 2, since the sericin metal complex as the flocculation agent coagulative precipitation most sericine in the wastewater from silk reeling, thereby reduced the chemical nutritional requirement (COD) of waste water, its maximum has decreased by 70%, has played vital role to purifying water.Contrasting various treatment condition can find, through the waste water after the processing of sericin ferrous metal complex compound, the reduction percentage of its COD value is handled much bigger than sericin, has illustrated that also the ability of sericin iron complex flocculation sediment protein and reduction waste water chemistry nutritional requirement is stronger.
Thereby remove in the experiment of metal ion purifying sericine in the sericin at weak acid scrubbing, measured the relation (seeing attached list 3) between different treatment time and the metal ion decreasing ratio, carried out 1 hour, 12 hours processing respectively handling the throw out that obtains with zinc metal ion sericin complex compound.Adopt thermogravimetric analysis to carry out the remaining situation mensuration of metal ion in the throw out indirectly, sample is separated 600 ℃ of punishment and is finished, to locate the weight survival rate at 600 ℃ be 27.55% to Shi Yan pure silk glue protein as a comparison, and to locate the weight survival rate at 600 ℃ be 51.66% and do not carry out metal ion sericin complex compound that diluted acid handles.It is 32.39% that the throw out of being handled 1 hour by diluted acid is located the weight survival rate at 600 ℃, and it is 26.49% that the throw out of handling 12 hours is located the weight survival rate at 600 ℃.Get rid of the thermogravimetric analysis experimental error, the material of throw out after having handled 2～12 hours located the weight survival rate at 600 ℃ and located the weight survival rate with the pure silk glue protein at 600 ℃ and equate, shows that metal ion deviates from fully.
Conclusion
1, the sericin metal complex is as the flocculation functional materials, can coagulative precipitation silk enterprise wastewater in most sericine, reduce the protein concn in the waste water, reduce waste water chemistry nutritional requirement, purify water.
2, find by control experiment, sericine itself is because peptide bond, hydrogen bond action etc. between protein, also can reduce protein content in the waste water by stirring contact precipitation, but its sedimentary speed is quite slow, approximately need 48-72 hour, practicality is relatively poor.And the ability of sericin metallic iron complex compound flocculation sediment protein and reduction waste water chemistry nutritional requirement (COD) is strong, and the speed that staticly settles after its stir process is also very fast, only needs about 12 hours, is suitable for large-scale production line.Sericin metal complex and sericin are as flocculation agent, and the ability of protein and reduction waste water chemistry nutritional requirement (COD) is directly proportional with its input amount in waste water in its flocculation sediment waste water.
3, use the sericin metal complex to flocculate and extract sericin in the silk enterprise wastewater; the sericin that extracts can partly enter purification phase; another part continues to use in wastewater treatment as the flocculation functional materials, and is significant for water resources protection, protein utilization of waste material etc.
Subordinate list 1: the protein content before and after the waste water flocculating precipitation process
| Flocculation agent | Sericin Fe metal complex | Sericine | The check plot | ||||
| Flocculation agent/waste water (mg/ml) | 10/5 | 20/5 | 30/5 | 10/5 | 20/5 | 30/5 | 0/5 |
| Protein content (mg/ml) in the waste water before handling | 8.450 | 8.450 | 8.450 | 8.450 | 8.450 | 8.450 | 8.450 |
| Protein content mg/ml in the processed waste water | 4.391 | 3.727 | 3.469 | 6.255 | 5.129 | 4.446 | 8.450 |
| Front and back poor (mg/ml) | 4.059 | 4.723 | 4.981 | 2.195 | 3.321 | 4.004 | 0 |
| The range of decrease (%) | 48.03 | 55.89 | 58.95 | 25.98 | 39.30 | 47.38 | 0 |
Subordinate list 2: the chemical oxygen demand (COD) of waste water before and after flocculation sediment is handled
| Flocculation agent | Sericin Fe metal complex | Sericine | The check plot | ||||
| Flocculation agent/waste water (mg/ml) | 10/5 | 20/5 | 30/5 | 10/5 | 20/5 | 30/5 | 0/5 |
| COD value (mg/L) before handling | 359.2 | 359.2 | 359.2 | 359.2 | 359.2 | 359.2 | 359.2 |
| Handle back COD value (mg/L) | 252.0 | 135.2 | 105.6 | 323.2 | 289.6 | 254.0 | 359.2 |
| COD reduces per-cent | 29.84％ | 62.36％ | 70.60％ | 10.02％ | 19.38％ | 29.29％ | 0 |
Subordinate list 3: thermogravimetric analysis data results
| Silk gum | Contain (Zn 2+) throw out acid treatment 1 hour | Contain (Zn 2+) throw out acid treatment 12 hours | Contain (Zn 2+) throw out do not carry out acid treatment | |
| First decomposition temperature (℃) | 189.47 | 206.33 | 207.37 | 203.76 |
| Second decomposition temperature (℃) | 299.30 | 291.30 | 291.25 | 291.40 |
| 600 ℃ of weight survival rates (%) | 27.55 | 32.39 | 26.49 | 51.66 |
Claims (4)
1. the treatment process of waste water containing sericin protein, it is characterized in that: it comprises the steps:
1. at first prepare the sericin metal complex;
2. the sericin metal complex that makes is added as flocculation agent and contain in the waste water of sericin, the add-on of sericin metal complex is 2～10 milligrams in every milliliter of waste water, the above-mentioned container that waste water and flocculation agent are housed is put into the constant temperature water bath shaking table, water temperature remains on about 25～35 ℃, make its oscillatory reaction 6～10 hours, extract throw out;
3. in the throw out that obtains, add weak acid scrubbing, with magnetic stirrer after 1～12 hour centrifugal gained drying precipitate be sericin powder.
2. the treatment process of waste water containing sericin protein according to claim 1, it is characterized in that: the sericin metal complex of described the first step preparation is a transition metal complex, its preparation method is: obtain sericin purification solution-use soxhlet extraction device earlier, with ether the cocoon shell is carried out 24～48 hours cycling extractions or immersion treatment to remove waxy substance wherein, boil with ethanol again after the distilled water wash drying and removed carbohydrate and ash content in 0.5～1.5 hour, clean dry, in pure water, boiled again 2～4 hours, remove fiber, remaining thick liquid is silk gum solution, is that the thick back of 5～7mg/ml is stand-by with the sericin solution concentration that obtains to its concentration;
The preparation of sericin metal complex-adding metal chlorate solution or solution of metal sulfates and KCl solution in the above-mentioned sericin purification solution that obtains, its add-on is: add the metal chlorate solution of 0.25mol/L or the KCl solution 3.25ml of solution of metal sulfates 3.25ml and 2.5mol/L in every 100ml sericin purification solution, with concentration is the KOH solution adjusting pH value of 0.05mol/L, add KOH solution while stirring, make PH＞9.1, make coordination reach balance with magnetic stirrer, it is standby that filtration obtains metal complex.
3. the treatment process of waste water containing sericin protein according to claim 2, it is characterized in that: described metal chlorate is FeCl
3, ZnCl
2, CoCl
2Or CuCl
2
4. according to the treatment process of claim 1 or 2 or 3 described waste water containing sericin proteins, it is characterized in that: described diluted acid is dilute hydrochloric acid or sparse acid, and its concentration is 0.00lmol/ml, and the add-on of diluted acid is 1.5～3 milliliters in every milliliter of throw out.
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|---|---|---|---|
| CNB2007100930918A CN100506840C (en) | 2007-11-30 | 2007-11-30 | Method for treating waste water containing sericin protein |
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| Publication Number | Publication Date |
|---|---|
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| CN100506840C CN100506840C (en) | 2009-07-01 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084065A (en) * | 2013-01-14 | 2013-05-08 | 天津工业大学 | Ultra-filtration membrane removing method of metal ions |
| CN103242440A (en) * | 2013-05-03 | 2013-08-14 | 广西立盛茧丝绸有限公司 | Sericin extracting method |
| CN101575371B (en) * | 2009-05-13 | 2013-09-18 | 桂林奥尼斯特节能环保科技有限责任公司 | Method for adopting tannin to process silkworm cocoon processing wastewater and recycle sericin protein |
| CN108221173A (en) * | 2018-01-26 | 2018-06-29 | 徐州光彩丝绵制品有限公司 | A kind of high-efficiency antimicrobial silk wadding quilt and preparation method thereof |
| CN108409848A (en) * | 2018-03-07 | 2018-08-17 | 西南大学 | The preparation method and applications of sericin polypeptide |
| CN115784319A (en) * | 2022-11-16 | 2023-03-14 | 科立鑫(珠海)新能源有限公司 | Spherical cobalt carbonate particles and preparation method thereof |
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2007
- 2007-11-30 CN CNB2007100930918A patent/CN100506840C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575371B (en) * | 2009-05-13 | 2013-09-18 | 桂林奥尼斯特节能环保科技有限责任公司 | Method for adopting tannin to process silkworm cocoon processing wastewater and recycle sericin protein |
| CN103084065A (en) * | 2013-01-14 | 2013-05-08 | 天津工业大学 | Ultra-filtration membrane removing method of metal ions |
| CN103242440A (en) * | 2013-05-03 | 2013-08-14 | 广西立盛茧丝绸有限公司 | Sericin extracting method |
| CN103242440B (en) * | 2013-05-03 | 2015-09-16 | 广西立盛茧丝绸有限公司 | A kind of Extraction Method for Sericin |
| CN108221173A (en) * | 2018-01-26 | 2018-06-29 | 徐州光彩丝绵制品有限公司 | A kind of high-efficiency antimicrobial silk wadding quilt and preparation method thereof |
| CN108409848A (en) * | 2018-03-07 | 2018-08-17 | 西南大学 | The preparation method and applications of sericin polypeptide |
| CN115784319A (en) * | 2022-11-16 | 2023-03-14 | 科立鑫(珠海)新能源有限公司 | Spherical cobalt carbonate particles and preparation method thereof |
| CN115784319B (en) * | 2022-11-16 | 2023-08-22 | 科立鑫(珠海)新能源有限公司 | Spherical cobalt carbonate particles and preparation method thereof |
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