CN104445336A - Method and apparatus for producing pure CaCl2 crystal - Google Patents
Method and apparatus for producing pure CaCl2 crystal Download PDFInfo
- Publication number
- CN104445336A CN104445336A CN201410472771.0A CN201410472771A CN104445336A CN 104445336 A CN104445336 A CN 104445336A CN 201410472771 A CN201410472771 A CN 201410472771A CN 104445336 A CN104445336 A CN 104445336A
- Authority
- CN
- China
- Prior art keywords
- crystallization
- cacl
- nacl
- evaporation
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/32—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The object of the present invention is to provide a method and an apparatus for producing pure CaCl2 crystals from a NaCl-contaminated raw CaCl2-containing aqueous solution, and the content of the contamination NaCl is below 2%. NaCl crystals are separated from the solution through respective separation devices (3) of a pre-concentration device (1) and high concentration device (2), CaCl2 tetrahydrates are preferably formed in a cooling crystallization device (4) and then enter into a dissolving device for dissolving, and the fused CaCl2 passes a prilling granulator (6) to form the desired pure CaCl2 product.
Description
Technical field
The present invention relates to by the CaCl containing NaCl impurity
2original solution produces pure CaCl
2the method of crystallization, and the equipment implementing the method.
Background technology
Produce in waste solution, particularly soda product production process, this solution contains in a large number the CaCl of (such as about 10%)
2(all the other are H with the NaCl of a small amount of (such as 5%)
2o).% content can be interpreted as mass percentage content below all the time.Also may other impurity be contained, as CaSO in this solution
4or MgCl
2, but do not consider within the scope of the invention, be not therefore also mentioned.
Interestingly, described waste solution is processed, can conveniently produce the CaCl that can be used for other purposes, can sell
2crystallization.Have recently emerged a large amount of by will CaCl be rich in
2original solution first carry out pre-concentration, then carry out the method for high enrichment, equally also can form NaCl crystallization in the process.Sometimes in bantam, this concentration process can be undertaken by independent enrichment step.The NaCl crystallization formed in this concentration process can be separated by filtration or centrifugation.The high density CaCl of such generation
2solution can produce CaCl by tablets press
2particle.The product that this mode produces, due to NaCl and CaCl
2solubleness in water, usually will inevitably produce content higher than 2% NaCl impurity.
But, sometimes for CaCl
2the NaCl impurity allowed in particle has higher requirement.Therefore in some cases, require that the operator of manufacturer ensures the CaCl of device fabrication
2in crystalline product, the content of NaCl impurity must lower than 2% (CaCl
2the ratio of/NaCl is at least 50), even lower than 1.5% (CaCl
2the ratio of/NaCl is at least 65.7).Production method known today there is no method and ensures this point.
Summary of the invention
Task of the present invention is to provide with a kind of by the CaCl containing NaCl impurity
2original solution produces pure CaCl
2the method of crystallization, the method can ensure that NaCl impurity contained by product is lower than 2%; The present invention also further provides the equipment implementing the method.
The method feature that this task is mentioned by claim 1 realizes; Preferably, the method feature is proposed further by claim 2-11; Implement the feature according to the equipment of method of the present invention with claim 12, preferably, this feature is proposed further by claim 13-18.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the equipment implementing the inventive method.By the schematic diagram shown in following Fig. 1, further illustrate equipment of the present invention.In Fig. 1, pre-concentration device 1, high enrichment device 2, tripping device 3, condensation-crystallization device 4, melting appartus 5, prilling granulator 6.
Embodiment
Containing such as 5%NaCl impurity and 10%CaCl
2aqueous solution S, by evaporation unit 1 by solution pre-concentration.In order to reach energy-conservation object, water vapour is by multistage, and the evaporation unit 1 that every one-level has different operating temperature obtains, and wherein the evaporation of the particularly first step, preferably realizes by means of decompression.The classification working temperature of pre-concentration process is preferably placed between about 135-55 DEG C.Preferably, described pre-concentration process makes the CaCl in solution
2mass content reaches about 40-46%.By removing moisture, NaCl being reached capacity the limit, therefore making the NaCl crystallization of considerable part from solution, be separated (such as by filtering, not shown) in this process and extracting.CaCl
2in solution, the ratio of NaCl is fewer and feweri, preferably, again by the evaporation unit 2 of the multistage formation of similar evaporation unit 1 by water vapour high enrichment further.In addition, from the solution of pre-concentration, crystallization goes out more part of NaCl, then by ensuing tripping device 3, preferred filtration unit is separated, and on purpose reenters evaporation unit 1, is no longer emanated, therefore, it is possible to improve the output of NaCl, carry out coml utilization.The classification working temperature of the high enrichment process of evaporation unit 2, is preferably placed between about 145-60 DEG C.
The filtrate of tripping device 3 is by condensation-crystallization device 4, wherein CaCl
2in solution, the ratio of NaCl is reduced further.In order to reduce CaCl in water
2high-dissolvability, reduce temperature and remove moisture and making it to reach capacity, making CaCl
2crystallize out with the form of crystalline hydrate.In addition be with being worth special instruction, in condensation-crystallization process, CaCl
2the form formation that crystalline hydrate Yi Ershui, four water or six water etc. are different, main formation four water crystallization of calcium chloride hydrate (CaCl
2.4H
2o).The temperature of condensation-crystallization process needs between about 30-45 DEG C, preferred 30-35 DEG C.Temperature higher in condensation-crystallization process can form two pure water crystallization hydrates equally, and this crystalline hydrate is difficult to separate from solution relatively.Lower temperature can form six water crystallization hydrates, is separated very well, because high-moisture needs to be further processed crystal, Energy harvesting has shortcoming although this crystalline hydrate particle is very large.Most suitable is the granular crystal with four water crystallization hydrates of obviously few water content of same generation.CaCl in condensation-crystallization device 4 mother liquor
2crystalline hydrate is separated by strainer (not shown), and the residue NaCl contained discharges by the partial discharge of mother liquor, preferably gets back in evaporation unit 2, avoids the increase of NaCl concentration.
The CaCl separated
2crystalline hydrate enters into melting appartus 5 and melts.Once there are two water crystallization hydrates of noticeable certain scale in fusion process, then suggestion adds H
2o (not shown).The thermal crystalline solution produced in dissolving apparatus 5 will be introduced in solid-state production equipment, in the apparatus along with the evaporation of moisture, and the CaCl existed in solid form desired by formation
2product.Solid-state production equipment is preferably made up of prilling granulator (6), such as thermopnore tablets press or belt tablets press; It also may be the solid-state production equipment (such as particle, powdery, bulk) that other arbitrary and solution adapt.
Need within the scope of the invention, it is again noted that the concentration process of the solution that NaCl is separated, by single-stage concentration process, water to be evaporated completely.But, for main equipment, preferably there is multistage concentrating unit.
Following examples show the action effect according to method of the present invention, with background technology unlike, according to CaCl of the present invention
2the production of crystalline product is not directly by CaCl
2solution granulation, but by CaCl
2crystalline hydrate dissolves.
Containing the 10%CaCl that has an appointment
2with the original solution (CaCl of 5%NaCl
2the ratio of/NaCl is 20) in pre-concentration device according to the present invention, by the evaporation of moisture and being separated of NaCl, produce containing the 41%CaCl that has an appointment
2with the original solution (CaCl of 2%NaCl
2the ratio of/NaCl is 20.5).The solution of pre-concentration next in evaporation unit by high enrichment, produce containing the 55%CaCl that has an appointment
2with the solution (CaCl of 1.2%NaCl
2the ratio of/NaCl is 45.8) (after filtering).The temperature about 33 DEG C that next solution of high enrichment be subject in condensation-crystallization device, wherein forms four water crystallization of calcium chloride hydrates in mother liquor.Relatively oarse-grained four water crystallization of calcium chloride hydrates can be separated by centrifugation without barrier, then enter into melting appartus, by constantly stirring fusing.The melting sodium-chlor of such generation joins in belt tablets press, produces CaCl
2crystalline product, this product water ratio 5%, containing the 94%CaCl that has an appointment
2with 1%NaCl (CaCl
2the ratio of/NaCl is 94).Therefore, it is possible to be starkly lower than the maximum contaminant content value of required crystalline product, namely NaCl content is less than 2%.
Being preferably four water crystallization of calcium chloride hydrates according to the most obvious advantage of method of the present invention, particularly crystallization of calcium chloride, can it is evident that, by utilizing minimum additional energy, higher product purity can be reached.
Claims (18)
1. one kind by the CaCl containing NaCl impurity
2original solution produces pure CaCl
2the method of crystallization, comprises the following step:
---original solution, by the evaporation of moisture, concentrates and forms NaCl crystal;
---separation and extraction is out from solution for the NaCl crystal of formation;
---the CaCl obtained
2highly concentrated solution forms moisture CaCl by condensation-crystallization process
2crystallization;
---this moisture CaCl
2crystallization is separated and melt;
---the heat fusing calcium chloride of formation is introduced in solid-state production equipment, particularly prilling granulator, the CaCl desired by formation
2crystallization.
2. method according to claim 1, is characterized in that, described concentration process is multistage, comprises multistage pre-concentration process and multistage high enrichment process subsequently, is wherein extracted by NaCl crystal in multistage pre-concentration process.
3. method according to claim 2, is characterized in that, by the evaporation of moisture in described high enrichment process, forms NaCl crystal further, is separated and delivers to pre-concentration device from highly concentrated solution.
4. the method according to claim 1-3, is characterized in that, described NaCl is realized from the separation of highly concentrated solution by strainer.
5. the method according to claim 1-4, is characterized in that, the solution that the part produced in described condensation-crystallization process contains NaCl sends back in highly concentrated solution.
6. the method according to claim 1-5, is characterized in that, CaCl in described condensation-crystallization process
2main with the form crystallization of four water crystallization of calcium chloride hydrates.
7. the method according to claim 1-6, is characterized in that, the temperature of described condensation-crystallization process needs between about 30-46 DEG C, preferred 30-35 DEG C.
8. the method according to claim 1-7, is characterized in that, described pre-concentration process need multistage evaporation, and wherein single-stage working temperature is different from other grade, preferably between about 135-65 DEG C.
9. the method according to claim 1-8, is characterized in that, CaCl in the solution that described pre-concentration process obtains
2mass content is about 40-45%.
10. the method according to claim 1-9, is characterized in that, described high enrichment process need multistage evaporation, and wherein single-stage working temperature is different from other grade, preferably between about 145-80 DEG C.
11. according to Claim 8-10 method, it is characterized in that, described pre-concentration process and high enrichment process one-level evaporation heating, by means of decompression realize.
12. 1 kinds of equipment implementing method according to claim 1, comprise with lower part:
---the solution containing impurity, NaCl crystallization is discharged by the evaporation of water vapour by it,
---by NaCl Crystallization Separation tripping device out (3),
---the condensation-crystallization device (4) be connected with the taphole of tripping device (3),
---with the CaCl of condensation-crystallization device (4)
2crystallization exports the melting appartus (5) be connected,
---the solid-state production equipment be connected with melting appartus (5), particularly produce pure CaCl
2the prilling granulator (6) of crystallization.
13. equipment according to claim 12, it is characterized in that, the evaporation of described water vapour is realized by first evaporation unit (1) of pre-concentration device and second evaporation unit (2) of high enrichment device that is connected with the first evaporation unit (1).
14. equipment according to claim 13, is characterized in that, described first evaporation unit (1) is made up of multistage.
15. equipment according to claim 13-14, it is characterized in that, the second evaporation unit (2) is made up of multistage.
16. equipment according to claim 13-15, is characterized in that, the heating of described evaporation unit (1,2) certain one-level evaporation, realizes by means of decompression.
17. equipment according to claim 13-16, it is characterized in that, described tripping device (3) is made up of strainer.
18. equipment according to claim 13-17, it is characterized in that, described prilling granulator (6) is thermopnore tablets press or belt tablets press.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102013110290.5 | 2013-09-18 | ||
| DE201310110290 DE102013110290A1 (en) | 2013-09-18 | 2013-09-18 | Process and plant for producing a pure CaCl 2 crystallizate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104445336A true CN104445336A (en) | 2015-03-25 |
| CN104445336B CN104445336B (en) | 2018-07-03 |
Family
ID=52579783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410472771.0A Active CN104445336B (en) | 2013-09-18 | 2014-09-16 | Pure CaCl2The production method and equipment of crystallization |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN104445336B (en) |
| DE (1) | DE102013110290A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011816A (en) * | 2022-06-02 | 2022-09-06 | 紫金矿业集团股份有限公司 | Method for recovering lithium from salt field calcium chloride crystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342611A (en) * | 2001-09-28 | 2002-04-03 | 岳中州 | Process for preparing granular calcium chloride and its sphericizing granulator |
| CN1903729A (en) * | 2006-08-08 | 2007-01-31 | 河北银山精制碘盐有限责任公司 | Comprehensive utilization method of sea salt bittern |
-
2013
- 2013-09-18 DE DE201310110290 patent/DE102013110290A1/en active Pending
-
2014
- 2014-09-16 CN CN201410472771.0A patent/CN104445336B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342611A (en) * | 2001-09-28 | 2002-04-03 | 岳中州 | Process for preparing granular calcium chloride and its sphericizing granulator |
| CN1903729A (en) * | 2006-08-08 | 2007-01-31 | 河北银山精制碘盐有限责任公司 | Comprehensive utilization method of sea salt bittern |
Non-Patent Citations (3)
| Title |
|---|
| 刘美云等: ""NaCl一CaCl2体系水溶液蒸发浓缩过程中浓度变化与沸点关系的研究"", 《盐业与化工》 * |
| 张顺达等: ""综合利用碱厂废液联产盐钙"", 《化工环保》 * |
| 陈松等: ""化工产品熔融造粒技术及其应用"", 《中国粉体技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115011816A (en) * | 2022-06-02 | 2022-09-06 | 紫金矿业集团股份有限公司 | Method for recovering lithium from salt field calcium chloride crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104445336B (en) | 2018-07-03 |
| DE102013110290A1 (en) | 2015-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2827921C (en) | Selective salt recovery from mixed salt brine | |
| CN102502720A (en) | Process for producing battery-grade lithium carbonate through processing carbonate type lithium concentrate by deep carbonation method | |
| CN103318923B (en) | Method for recovering sodium sulfate from white carbon black mother solution | |
| KR20140031195A (en) | Method and device for recovering boric acid | |
| CN104310444A (en) | Method for extracting potassium nitrate from waste potassium nitrate raw material in production of chemically-toughened glass | |
| JP2009196849A (en) | Silicon recovery method and silicon recovery apparatus | |
| CN102642837B (en) | Method for recycling polysilicon from silicon wafer waste slurry cut by diamond wire saw | |
| CN104445336A (en) | Method and apparatus for producing pure CaCl2 crystal | |
| CN104030261B (en) | A kind of production method of high purity electron-level phosphoric acid | |
| CN101125892A (en) | Method for producing aminoglucose hydrochloride | |
| CN101219946A (en) | Method for recycling waste liquor of ammonium hexanedioic acid and recycling system thereof | |
| CN101767803A (en) | Food-grade potassium chloride production process | |
| CN1944241B (en) | Process for producing high purity crystalline sodium sulfide | |
| CN111020632B (en) | Method for recovering electrolytic fluorine waste electrolyte | |
| CN102633293B (en) | Method for refining multistage circulation evaporation-free copper sulfate | |
| EP2661414A1 (en) | Process for the purification of phosphoric acid | |
| CN111422914A (en) | Production method of granular crystalline ferric chloride | |
| JP6103017B2 (en) | Nickel sulfate crystallization equipment and crystallization method | |
| TW202135908A (en) | Method for separating soluble salts contained in a residue containing at least three salts | |
| CN101973840A (en) | Method for separating durene by freezing crystallization | |
| CN114684834A (en) | Method for extracting lithium from clay type lithium ore | |
| JP6417963B2 (en) | Method and apparatus for processing collected boiler ash | |
| JP2015521583A (en) | Method for purifying silicon | |
| KR101223384B1 (en) | Apparatus and method for manufacturing lithium hexafluoro phosphate | |
| CN104445126A (en) | Coproduction method of anhydrous tripotassium phosphate, crystallographic tripotassium phosphate and calcium phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |