CN101948483A - Method for preparing calcium soap by utilizing quick lime and method for processing produced emulsified compound - Google Patents
Method for preparing calcium soap by utilizing quick lime and method for processing produced emulsified compound Download PDFInfo
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- CN101948483A CN101948483A CN2010102618405A CN201010261840A CN101948483A CN 101948483 A CN101948483 A CN 101948483A CN 2010102618405 A CN2010102618405 A CN 2010102618405A CN 201010261840 A CN201010261840 A CN 201010261840A CN 101948483 A CN101948483 A CN 101948483A
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Abstract
The invention relates to a method for preparing calcium soap by utilizing quick lime and a method for processing produced emulsified compound, in particular to a technical method for preparing calcium soap in a rare earth extraction section by utilizing quick lime. The method comprises the following steps: carrying out ammonia steaming-ammonia absorbing: carrying out dual firing and ammonia steaming on the quick lime or quick lime and ammonium chloride solution according to the molar ratio that n Ca<+>: n ammonium chloride =1: 1.5-2.2; absorbing the steamed ammonia gas by blank extracting agent to form ammonium soap; filtering or clarifying the reacted solution to obtain high concentration ammonia nitrogen calcium chloride solution; and carrying out phase inversion: mixing and stirring the ammonium soap with the high concentration ammonia nitrogen calcium chloride solution prepared by ammonia steaming-ammonia absorbing for 5-15 min, wherein the ammonium enters the aqueous phase to form ammonium chloride, the calcium enters the organic phase to form the calcium soap. In the invention, as the quick lime is adopted, the economic benefits are high, no three wastes is discharged and no pollution to the environment is generated; and meanwhile, consumption of the extracting agent can be reduced by more than 2/3 and the yield of the rare earth is improved.
Description
Technical field
A kind ofly prepare the treatment process of the emulsifying mixt of calcium soap and generation, belong to the method for using unslaked lime to prepare calcium soap in the extraction workshop section and the treatment process of the emulsifying mixt that produced with unslaked lime.This solvent extraction technology can be widely used in industrial sectors such as Rare Earth Separation, hydrometallurgy, petrochemical complex, nuclear industry, medicine, food and environmental protection.
Background technology
China's rare earth resources occupies first place in the world, industrial separation of rare earth elements extensively adopts solvent extraction (being a kind of method of utilizing organic solvent from its not miscible liquid phase certain material to be extracted) technology, promptly pass through strict process control, make the earth solution of certain flow and the extraction agent of certain flow, operations such as process mixing, extractive reaction, clarification, washing, back extraction in extraction tank, obtain surplus liquid and strip liquor, some needs further to separate, and mishmetal is separated into various single or enriched substance products the most at last.
In rare earth extraction technology, blank extraction agent such as P507, the P204 etc. of usefulness are to be principal character with the cationic exchange in extraction process usually, i.e. H in metal ion and the extraction agent
+Realize exchange.Because H
+Enter water and make and be extracted the solution pH value and descend, cause the loading capacity of extraction agent to reduce greatly, for addressing this problem, the saponification technology is widely used aborning, and the saponifying agent that adopts mostly is NaOH, NH at present
4OH and NH
4HCO
3But use this type of saponifying agent, will produce a large amount of brine wastes in the solvent extraction.This waste strength height, foreign matter content are low, because the price of this salt own is lower, are again by products, and cost recovery generally is higher than itself and is worth, thus recovery value and little, and end treatment difficulty relatively.The invention " rare earth extraction saponification waste-water recycle method " of Chinese patent (publication number is CN101549926) will add Na earlier in the waste water
2SO
3, BaCl
2, Na
2CO
3, refining through ion exchange resin again after the removal of impurities, Ca
2+, Mg
2+During≤20ppb, deliver to electrolysis workshop section again and generate hydrochloric acid and liquid caustic soda.This technology is wastewater treatment method, and is single from technology consideration itself, and energy consumption height, step are many.If can in saponification step, promptly solve wastewater problem then better.Actual, because solvent extraction technology not only is applied to Rare Earth Separation, also be applied to various industrial sectors such as hydrometallurgy, petrochemical complex, nuclear industry, medicine, food and environmental protection, so a kind of rational method of wastewater treatment especially is with a wide range of applications.
In addition, in the extraction production process, because a variety of causes, also have between the profit two-phase that the small amount of solid particulate is present in extraction section, form emulsion layer.This emulsion layer can be with the carrying out that produces thickening gradually, when reaching certain thickness, owing to produce the inevitable of fluctuation, this emulsion layer can have influence on the biphase separating effect, can cause when serious production be forced to stop, therefore, need in the production irregularly to extract out with siphonage.Though siphonage can solve the problem that a large amount of emulsification influences are produced,, caused the loss of a large amount of extraction agents along with the sucking-off and the discharging of siphonage with liquid substance.The price of used extraction agent is generally all than higher, so the consumption of extraction agent has taken big production cost in extraction is produced.The main consumption approach of extraction agent comprises: 1, sneak in the emulsification and taken away; 2, run, drip, leak; 3, volatilization; 4, be soluble in the aqueous phase.Sneak into wherein in the emulsification that to be taken away be the major cause that extraction agent consumes, can account for that extraction agent consumes more than 80%.
Summary of the invention
The technical problem to be solved in the present invention is: overcomes the deficiencies in the prior art, a kind of easy to operate, method that unslaked lime that the Rare Earth Separation coefficient is not had an influence prepares calcium soap is provided, and the method that the emulsifying mixt that it produced is handled.
The technical solution adopted for the present invention to solve the technical problems is: this is a kind of to prepare the method for calcium soap with unslaked lime, it is characterized in that: may further comprise the steps:
1.1 ammonia still process-suction ammonia: with unslaked lime or milk of lime and ammonium chloride solution n in molar ratio
Ca+: n
Ammonium chloride=1: 1.5～2.2 Hybrid Heating ammonia still processs absorb the formation ammonium soaps with the ammonia that steams with blank extraction agent; Reacted solution after filtration or the clarification after, obtain the ammonia nitrogen in high density calcium chloride solution;
1.2 phase inversion: gained ammonium soaps and ammonia nitrogen in high density calcium chloride solution are mixed, carry out repeatedly the phase inversion reaction, each churning time is 5～15min, and ammonium enters water and forms ammonium chloride solution, and calcium enters and forms calcium soap in the organic phase;
1.3 reclaim: with step 1.2 gained ammonium chloride solution recovery carrying out once more step 1.1 ammonia still process-suction ammonia react.
The described blank catalyzer of step 1.1 is P507 or P204, and consumption is 2～10L, and concentration is 0.8～1.8mol/L.
The saponification deg of the calcium soap that step 1.2 makes is 25～35%.
Water described in the step 1.2 is the ammonia nitrogen in high density calcium chloride solution, and add-on is 20ml/ time; Organic phase is an ammonium soaps, and add-on is 80ml/ time.
A kind ofly prepare the treatment process of the emulsifying mixt that calcium soap produces by unslaked lime, it is characterized in that: the emulsifying mixt that produces is extracted out from cell body, carried out mechanical filter by 100～400 order filter clothes, gained filtrate is thrown in and is continued reaction in the cell body.
After the emulsifying mixt that produces extracted from cell body, the employing cascade filtration.
The processing of emulsifying mixt as the additional technology of the method for preparing calcium soap with unslaked lime, can be made up utilization with the calcium soap preparation method, also can be separately as using in operation technology that will handle emulsifying agent of what is the need in office.
In rare earth extraction technology, need carry out saponification to blank extraction agent usually and handle, the saponifying agent of selecting for use is generally NaOH, NH
4OH and NH
4HCO
3In alkali, this type of blank extraction agent extraction process produces a large amount of brine wastes, owing to the price of this salt own is lower, is again by product, and cost recovery generally is higher than itself and is worth, thus recovery value and little, and also end treatment is relatively more difficult.The present invention at first selects lime (CaO) or milk of lime (Ca (OH) for use
2) and ammonium chloride (NH
4Cl) solution reaction is with the ammonia (NH that makes
3) absorb acquisition ammonium soaps (NH with blank catalyzer
4A), reacted water after filtration or the clarification after, obtain the ammonia nitrogen in high density calcium chloride solution, its reaction formula is:
CaO+H
2O＝Ca(OH)
2，
2NH
4Cl+Ca(OH)
2＝2NH
3↑+CaCl
2+2H
2O，
NH
3+HA＝NH
4A。
Again the ammonia nitrogen in high density calcium chloride solution that makes in ammonium soaps and the above-mentioned ammonia still process-suction ammonia is mixed, carry out the phase inversion reaction.Wherein, ammonium enters water and forms ammonium chloride solution, and calcium enters and forms calcium soap in the organic phase.Calcium soap is as the extraction agent separation of rare earth elements.The reaction formula that relates to is:
2NH
4A+CaCl
2＝CaA
2+2NH
4Cl，
3CaA
2+2RECl
3＝2REA
3+3CaCl
2。
Because the enforcement calcium soap has the compound of many calcium water insoluble, emulsification can increase in the production line, is able to the prerequisite of smooth implementation so the treatment process of good emulsifying thing is a calcium soap.For achieving the above object, in view of emulsification is a solia particle, organic phase and water are liquid, so the present invention adopts the method for mechanical filter that emulsification is removed.Specifically be to filter through the mixture behind the phase inversion, to comprise water and organic phase in the filtrate, to return the extracting position; Filter cake is an emulsifying mixt, can return comprehensive utilization.This method has realized the recycle of extraction agent, has saved production cost.
After testing, prepare the method for calcium soap and the treatment process of emulsification thereof by of the present invention with unslaked lime, the surplus liquid of the product of gained and strip liquor ammonia-nitrogen content＜10ppm, the existing technology of ammonia-nitrogen content obviously reduces, and, show that this technology do not have influence to the Rare Earth Separation coefficient by the measuring and calculating ree distribution pattern.
Compared with prior art, a kind of beneficial effect that treatment process had for preparing the emulsifying mixt of calcium soap and generation with unslaked lime of the present invention is:
1. there is not environmental issue in this preparation method three-waste free discharge;
2. use unslaked lime to make saponifying agent, low price produces byproduct calcium chloride simultaneously, the economic benefit height;
3. pass through the processing to the emulsifying mixt that produces, the consumption that can reduce extraction agent improves the rare earth yield more than 2/3 simultaneously;
4. this technological operation is simple, running cost is low, and is connected convenient with existing technology and production unit, and production and Rare Earth Separation coefficient are not had influence.
Description of drawings
Fig. 1 is the process flow sheet that unslaked lime of the present invention prepares the method for calcium soap.
Fig. 2 is three a stage countercurrents extraction separating funnel phase inversion sepn process synoptic diagram.
Wherein: 1., 2. be two separating funnels, F: water, O: organic phase.
The present invention will be further described below in conjunction with accompanying drawing 1～2:
Embodiment
Embodiment 1
Processing parameter is as follows:
Get that concentration is the ammonium chloride waste-water of 4mol/L: 200ml on the production line; Technical grade unslaked lime: 30g; Concentration is the blank P507 (organic phase) of 1.5mol/L: 3.0L.
With reference to accompanying drawing 1～2, processing step is as follows:
A, ammonia still process-suction ammonia
In matrass, (CaO) mixes with ammonium chloride waste-water with unslaked lime, heating ammonia still process.Is the blank P507 absorption formation ammonium soaps of 1.5mol/L with the ammonia that steams with 3.0L concentration, and titrimetry ammonium soaps saponification deg is 25%; Reacted solution after filtration or the clarification after, obtain the ammonia nitrogen in high density calcium chloride solution.
B, phase inversion
Ammonium soaps and ammonia nitrogen in high density calcium chloride solution are added mixing stirring back static layering in the separating funnel.Carry out the phase inversion operation one by one, the concussion time is 10min at every turn, and water F is the ammonia nitrogen in high density calcium chloride solution, and add-on is 20ml/ time; Organic phase O is an ammonium soaps, and add-on is 80ml/ time.After the operation of 10 phase inversions, make the calcium soap (in No. 1 separating funnel of accompanying drawing 2 the 10th row) after the balance, measure to such an extent that the calcium soap saponification deg is 25%.
C, recovery: with phase inversion gained ammonium chloride solution recovery carrying out again ammonia still process-suction ammonia react.
The processing of d, emulsification: extract 100 liters of emulsifications out with siphonage from cell body, with 300 order filter clothes this emulsification is filtered, filtrate is returned extraction point, and filter cake reclaims comprehensive utilization.Contain 78 liters of feed liquids (water) in the actual measurement 95L filtrate; 17 liters of extraction agents (organic phase).
Embodiment 2
Processing parameter is as follows:
Get that concentration is the ammonium chloride waste-water of 4mol/L: 300ml on the production line; Milk of lime: 40g; Concentration is the blank P507 (organic phase) of 0.8mol/L: 10.0L.
Processing step is as follows:
A, ammonia still process-suction ammonia
In matrass, with milk of lime (Ca (OH)
2) mix heating ammonia still process with ammonium chloride waste-water.Is the blank P507 absorption formation ammonium soaps of 0.8mol/L with the ammonia that steams with 10.0L concentration, and measuring the ammonium soaps saponification deg is 35%; Reacted solution after filtration or the clarification after, obtain the ammonia nitrogen in high density calcium chloride solution.
B, phase inversion
Ammonium soaps and ammonia nitrogen in high density calcium chloride solution are added mixing stirring back static layering in the separating funnel.Carry out the phase inversion operation one by one, the concussion time is 15min at every turn, and water F is the ammonia nitrogen in high density calcium chloride solution, and add-on is 20ml/ time; Organic phase O is an ammonium soaps, and add-on is 80ml/ time.After the operation of 10 phase inversions, make the calcium soap after the balance, measure to such an extent that the calcium soap saponification deg is 35%.
C, recovery: with phase inversion gained ammonium chloride solution recovery carrying out again ammonia still process-suction ammonia react.
The processing of d, emulsification: from cell body, extract 100 liters of emulsifications out with siphonage, with 100 orders and 400 order filter clothes respectively should-emulsification carries out secondary filtration, filtrate is returned extraction point, filter cake reclaims comprehensive utilization.Contain 67 liters of feed liquids (water) in the actual measurement 86L filtrate; 19 liters of extraction agents (organic phase).
Embodiment 3
Processing parameter is as follows:
Get that concentration is the ammonium chloride waste-water of 4mol/L: 250ml on the production line; Technical grade unslaked lime: 35g; Concentration is the blank P204:6.0L of 1.0mol/L, and concentration is (LaCe) Cl of 1.2mol/L
3Feed liquid: 20ml.
Processing step is as follows:
A, ammonia still process-suction ammonia
In matrass, unslaked lime is mixed heating ammonia still process with ammonium chloride waste-water.Is that the blank P204 of 1.0mol/L absorbs the formation ammonium soaps with the ammonia that steams with 6.0L concentration, and actual measurement ammonium soaps saponification deg is 32%; Reacted solution after filtration or the clarification after, obtain the ammonia nitrogen in high density calcium chloride solution;
B, phase inversion
Ammonium soaps and ammonia nitrogen in high density calcium chloride solution are added mixing stirring back static layering in the separating funnel, carry out the phase inversion operation one by one, the concussion time is 5min at every turn, and water F is the ammonia nitrogen in high density calcium chloride solution, and add-on is 20ml/ time; Organic phase O is an ammonium soaps, and add-on is 80ml/ time.After the operation of 10 phase inversions, make the calcium soap after the balance, measure to such an extent that the calcium soap saponification deg is 32%.
C, recovery: with phase inversion gained ammonium chloride solution recovery carrying out again ammonia still process-suction ammonia react.
The processing of d, emulsification: extract 100 liters of emulsifications out with siphonage from cell body, respectively this emulsification is carried out secondary filtration with 100 orders and 300 order filter clothes, filtrate is returned extraction point, and filter cake reclaims comprehensive utilization.Contain 70 liters of feed liquids (water) in the actual measurement 90L filtrate; 20 liters of extraction agents (organic phase).
Getting the calcium soap 80ml after the balance that makes, repeatedly is (LaCe) Cl of 1.2mol/L with concentration
3Feed liquid 20ml carries out extractive reaction, when raffinate middle-weight rare earths concentration is constant till.Actual measurement load organic phases middle-weight rare earths concentration is 0.15mol/L.
Embodiment 4
Processing parameter is as follows:
Get that concentration is the ammonium chloride waste-water of 4mol/L: 180ml on the production line; Technical grade unslaked lime: 25g; Concentration is the blank P507 (organic phase) of 1.8mol/L: 2.0L, and concentration is the RECl of 1.7mol/L
3Mixed liquor: 50ml.
Processing step is as follows:
A, ammonia still process-suction ammonia
In matrass, (CaO) mixes with ammonium chloride waste-water with unslaked lime, heating ammonia still process.Is that the blank P507 of 1.8mol/L absorbs the formation ammonium soaps with the ammonia that steams with 2.0L concentration, and measuring the ammonium soaps saponification deg is 30%; Reacted solution after filtration or the clarification after, obtain the ammonia nitrogen in high density calcium chloride solution.
B, phase inversion
Carry out the phase inversion operation one by one in ammonium soaps and the ammonia nitrogen in high density calcium chloride solution adding separating funnel, the concussion time is 8min at every turn, and water F is the ammonia nitrogen in high density calcium chloride solution, and add-on is 20ml/ time; Organic phase O is an ammonium soaps, and add-on is 80ml/ time.After the operation of 10 phase inversions, make the calcium soap after the balance, measure to such an extent that the calcium soap saponification deg is 30%.
C, recovery: with phase inversion gained ammonium chloride solution recovery carrying out again ammonia still process-suction ammonia react.
The processing of d, emulsification: extract 100 liters of emulsifications out with siphonage from cell body, with 200 order filter clothes this emulsification is filtered, filtrate is returned extraction point, and filter cake reclaims comprehensive utilization.Contain 76 liters of feed liquids (water) in the actual measurement 92L filtrate; 16 liters of extraction agents (organic phase).
Get the calcium soap 80ml after the balance that makes, concentration is the RECl of 1.7mol/L
3Mixed liquor: 50ml, concussion 5min, static layering.Isolate surplus liquid, and with 6mol/L hydrochloric acid back extraction 2 times, strip liquor merges.Chemically examine the ree distribution pattern and the ammonia-nitrogen content of surplus liquid and strip liquor.Experimental result is as shown in the table: surplus liquid and strip liquor ammonia-nitrogen content＜10ppm.
The Rare Earth Separation coefficient is as shown in the table: by the measuring and calculating ree distribution pattern, show that this technology do not have influence to the Rare Earth Separation coefficient.
| Title | Computation process | The result | Normal value |
| βCe/La | (65.41×49.44)/(46.63×10.53) | 6.59 | 6.83 |
| βPr/Ce | (5.77×46.63)/(2.00×65.41) | 2.06 | 2.03 |
| βNd/Pr | (6.53×2.00)/(1.62×5.77) | 1.40 | 1.55 |
| βSm/Nd | (9.54×1.62)/(0.24×6.53) | 9.86 | 10.6 |
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment did, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (6)
1. one kind prepares the method for calcium soap with unslaked lime, it is characterized in that: may further comprise the steps:
1.1 ammonia still process-suction ammonia: with unslaked lime or milk of lime and ammonium chloride solution n in molar ratio
Ca+: n
Ammonium chloride=1: 1.5～2.2 Hybrid Heating ammonia still processs absorb the formation ammonium soaps with the ammonia that steams with blank extraction agent; Reacted solution after filtration or the clarification after, obtain the ammonia nitrogen in high density calcium chloride solution;
1.2 phase inversion: gained ammonium soaps and ammonia nitrogen in high density calcium chloride solution are mixed, carry out repeatedly the phase inversion reaction, each churning time is 5～15min, and ammonium enters water and forms ammonium chloride solution, and calcium enters and forms calcium soap in the organic phase;
1.3 reclaim: with step 1.2 gained ammonium chloride solution recovery carrying out once more step 1.1 ammonia still process-suction ammonia react.
2. according to claim 1ly prepare the method for calcium soap with unslaked lime, it is characterized in that: the described blank catalyzer of step 1.1 is P507 or P204, and consumption is 2～10L, and concentration is 0.8～1.8mol/L.
3. according to claim 1ly prepare the method for calcium soap with unslaked lime, it is characterized in that: the saponification deg of the calcium soap that step 1.2 makes is 25～35%.
4. according to claim 1ly prepare the method for calcium soap with unslaked lime, it is characterized in that: water described in the step 1.2 is the ammonia nitrogen in high density calcium chloride solution, and add-on is 20ml/ time; Organic phase is an ammonium soaps, and add-on is 80ml/ time.
5. one kind prepares the treatment process of the emulsifying mixt that calcium soap produces by unslaked lime, and it is characterized in that: the emulsifying mixt that produces is extracted out from cell body, carried out mechanical filter by 100～400 order filter clothes, gained filtrate is thrown in and continued reaction in the cell body.
6. according to claim 5ly prepare the treatment process of the emulsifying mixt that calcium soap produces, it is characterized in that by unslaked lime: after the emulsifying mixt that produces is extracted from cell body, the employing cascade filtration.
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|---|---|---|---|
| CN 201010261840 CN101948483B (en) | 2010-08-20 | 2010-08-20 | Method for preparing calcium soap by utilizing quick lime and method for processing produced emulsified compound |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205572A (en) * | 2013-04-25 | 2013-07-17 | 云南祥云飞龙有色金属股份有限公司 | Method for saponifying P204 |
| CN105755285A (en) * | 2016-05-04 | 2016-07-13 | 吉安鑫泰科技股份有限公司 | Saponifying and washing method of extracting agent |
| CN110950905A (en) * | 2019-12-11 | 2020-04-03 | 南昌航空大学 | Method for recovering P507 from waste P507 extraction organic phase |
| CN113403489A (en) * | 2021-06-17 | 2021-09-17 | 吉安鑫泰科技有限公司 | Calcium saponification organic phase clarification extraction process and equipment thereof |
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|---|---|---|---|---|
| CN1730681A (en) * | 2004-08-04 | 2006-02-08 | 胡建康 | Production method of acid extractant saponifying organic phase used in rare earth extraction separation |
| CN1891839A (en) * | 2005-07-04 | 2007-01-10 | 张宝藏 | Extracting agent for metal extraction, and its method and use |
| CN101121080A (en) * | 2007-05-15 | 2008-02-13 | 廖春生 | Method for preparing ammonia-calcium composite saponification agent and method for continuous saponification extracting |
| CN101168799A (en) * | 2006-10-27 | 2008-04-30 | 胡建康 | Extraction separation method for circularly preparing saponification organic phase rear earth from chloride solvent |
-
2010
- 2010-08-20 CN CN 201010261840 patent/CN101948483B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730681A (en) * | 2004-08-04 | 2006-02-08 | 胡建康 | Production method of acid extractant saponifying organic phase used in rare earth extraction separation |
| CN1891839A (en) * | 2005-07-04 | 2007-01-10 | 张宝藏 | Extracting agent for metal extraction, and its method and use |
| CN101168799A (en) * | 2006-10-27 | 2008-04-30 | 胡建康 | Extraction separation method for circularly preparing saponification organic phase rear earth from chloride solvent |
| CN101121080A (en) * | 2007-05-15 | 2008-02-13 | 廖春生 | Method for preparing ammonia-calcium composite saponification agent and method for continuous saponification extracting |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205572A (en) * | 2013-04-25 | 2013-07-17 | 云南祥云飞龙有色金属股份有限公司 | Method for saponifying P204 |
| CN103205572B (en) * | 2013-04-25 | 2014-09-03 | 云南祥云飞龙有色金属股份有限公司 | Method for saponifying P204 |
| CN105755285A (en) * | 2016-05-04 | 2016-07-13 | 吉安鑫泰科技股份有限公司 | Saponifying and washing method of extracting agent |
| CN110950905A (en) * | 2019-12-11 | 2020-04-03 | 南昌航空大学 | Method for recovering P507 from waste P507 extraction organic phase |
| CN113403489A (en) * | 2021-06-17 | 2021-09-17 | 吉安鑫泰科技有限公司 | Calcium saponification organic phase clarification extraction process and equipment thereof |
| CN113403489B (en) * | 2021-06-17 | 2023-01-24 | 吉安鑫泰科技有限公司 | Calcium saponification organic phase clarification extraction process and equipment thereof |
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| Publication number | Publication date |
|---|---|
| CN101948483B (en) | 2013-01-02 |
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