CN116161680A - Process for producing potassium chloride by using primary carnallite ore - Google Patents
Process for producing potassium chloride by using primary carnallite ore Download PDFInfo
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 title claims abstract description 132
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 71
- 239000001103 potassium chloride Substances 0.000 title claims abstract description 67
- 235000011164 potassium chloride Nutrition 0.000 title claims abstract description 67
- 239000002002 slurry Substances 0.000 claims abstract description 63
- 239000012452 mother liquor Substances 0.000 claims abstract description 56
- 238000002425 crystallisation Methods 0.000 claims abstract description 47
- 230000008025 crystallization Effects 0.000 claims abstract description 45
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 37
- 239000013505 freshwater Substances 0.000 claims abstract description 33
- 238000005188 flotation Methods 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000004090 dissolution Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 5
- 235000010755 mineral Nutrition 0.000 claims abstract description 5
- 239000011707 mineral Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 44
- 239000002562 thickening agent Substances 0.000 claims description 40
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 37
- 239000011591 potassium Substances 0.000 claims description 37
- 229910052700 potassium Inorganic materials 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 239000012141 concentrate Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010587 phase diagram Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000012267 brine Substances 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 230000002000 scavenging effect Effects 0.000 claims description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 27
- 239000011780 sodium chloride Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000005352 clarification Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- -1 insoluble matters Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0059—General arrangements of crystallisation plant, e.g. flow sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/02—Crystallisation from solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C21/00—Disintegrating plant with or without drying of the material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
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Abstract
The invention relates to a process for producing potassium chloride by using primary carnallite ore, belonging to the technical field of mineral separation. The method comprises the steps of coarse crushing, fine crushing, desliming, crystallization and fine crystal dissolution to obtain second-stage crystallizer underflow slurry, and then carrying out flotation, washing and drying to obtain a potassium chloride product. The invention adopts a decomposition crystallization process with two sections of crystallizers connected in series, thereby not only ensuring complete decomposition of carnallite and greatly reducing the fresh water addition amount of the decomposition crystallizer, but also greatly reducing the potassium chloride content in the externally discharged first-section decomposition mother liquor compared with the conventional decomposition process, and further improving the process recovery rate of the decomposition crystallization process; according to the invention, the overflow liquid of the first-stage crystallizer and the overflow liquid of the second-stage crystallizer are subjected to a fine crystal dissolving process, so that potassium chloride fine crystals contained in the overflow liquid of the crystallizer are recovered, the granularity of the product is increased, and the energy consumption of the subsequent dehydration and drying process is greatly reduced; the KCl content of the obtained potassium chloride product is more than or equal to 95 percent, and the recovery rate of the KCl process is more than or equal to 72 percent.
Description
Technical Field
The invention relates to a production process of potassium chloride, in particular to a process for producing potassium chloride by using primary carnallite, which is particularly suitable for underground potassium salt ores mainly comprising the primary carnallite in southeast Asia.
Background
Carnallite ore is the main raw material for producing potassium chloride, and the main impurity is sodium chloride. The method for producing potassium chloride by taking carnallite as a raw material at home and abroad mainly comprises the following three methods: a direct flotation process, a reverse flotation-cold crystallization process and a hot melt crystallization process.
The direct flotation method is classified into a cold decomposition-direct flotation method (using a general decomposition apparatus) and a cold crystallization-direct flotation method (using a decomposition crystallizer) according to whether or not a crystallization technique is used. The process is that carnallite is transported to a processing plant, a potassium chloride and sodium chloride mixture similar to potassium salt is obtained through hydrolysis, and then the separation of potassium chloride and sodium chloride is realized through adding a collector of potassium chloride by utilizing the difference of floatability of potassium chloride and sodium chloride. The process flow is simple and reliable, has strong adaptability to raw materials, but has low product quality and low process recovery rate.
The reverse flotation-cold crystallization method is to utilize the different water wetting capacities of the crystal surfaces of carnallite and sodium chloride, add sodium chloride flotation collector into carnallite pulp to increase the surface hydrophobicity of sodium chloride mineral, perform reverse flotation operation, remove sodium chloride in the carnallite pulp to obtain low-sodium carnallite, add the low-sodium carnallite into a crystallizer, add water to decompose and crystallize to obtain crude potassium, and wash and dry the crude potassium to obtain potassium chloride products. The method is a new advanced technology for producing potassium chloride at home and abroad, and the quality of potassium chloride products is complex, and the requirements on the quality of carnallite raw materials are high.
The carnallite is hydrolyzed into potassium chloride and sodium chloride at normal temperature by a hot melt crystallization method. And separating sodium chloride at high temperature and separating potassium chloride at low temperature by utilizing the different solubility of sodium chloride and potassium chloride at high temperature, and obtaining a potassium chloride product through washing and separation. After separating out potassium chloride, the mother liquor obtained by solid-liquid separation is heated and returned to the hot-melting process to dissolve the potassium chloride. The method has the advantages of high product quality, coarse crystal grain size, no flotation agent in the product, complex process flow, high energy consumption and serious corrosion to equipment.
At present, the forward flotation method, particularly the cold crystallization-forward flotation method, is widely applied to potassium chloride production, but in actual production, the carnallite decomposition crystallization process route is basically the same, a section of decomposition crystallization process is adopted, carnallite ore and fresh water are all added into a crystallizer at one time, and enough fresh water is required to be added to ensure complete decomposition of the carnallite, so that the decomposition water addition amount is larger, the potassium chloride content in the decomposition mother liquor is higher, meanwhile, the granularity of a potassium chloride product is smaller, and the average granularity is smaller than 0.10mm; in addition, the overflow of the crystallizer contains a large amount of fine crystals of potassium chloride, and a large amount of potassium chloride is discharged without being fully recovered, so that the recovery rate of the potassium chloride process is low, and therefore, a method capable of effectively improving the process yield of the potassium chloride produced by a positive flotation method is urgently needed.
The domestic carnallite ore is mainly obtained by sun-curing liquid ore (brine) in a salt field, the salt field production is mainly carried out by large-area deep water salt field water mining, and the impurities of the carnallite ore are mainly sodium chloride. Foreign, especially southeast Asia underground primary sylvite ore is mainly carnallite and contains stone salt and a small amount of sylvite. The raw carnallite ore is mixed with partial water insoluble matters, gypsum and other calcium-containing impurities in the process of ore formation and underground mining. The impurities such as insoluble matters, gypsum and the like are not easy to remove in the subsequent processing process, the produced potassium chloride product is grey, the purity of the potassium chloride is difficult to reach 98 percent (KCl percent), and the market competitiveness of the potassium chloride product is affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a process for producing potassium chloride by using primary carnallite ore, which has the advantages of simple process flow, low energy consumption, low production cost and easy large-scale industrialized implementation.
The technical problems to be solved by the invention are realized by the following technical scheme. The invention relates to a process for producing potassium chloride by using primary carnallite ore, which is characterized by comprising the following steps:
coarse crushing: crushing solid carnallite ore to a granularity below 25 mm;
finely divided: adding slurry mixing brine into the materials obtained in the step (A), and then sending the materials into a fine crusher for wet crushing, wherein the granularity of the finely crushed ores is less than or equal to 2mm;
desliming: feeding the materials obtained in the step (II) into desliming equipment to desliming, and removing insoluble mineral mud;
and (3) crystallizing: delivering the desliming material obtained in the step III to a carnallite decomposing and crystallizing device, wherein the decomposing and crystallizing device is formed by connecting a first-stage crystallizer and a second-stage crystallizer in series, carnallite slurry is firstly added into the first-stage crystallizer for decomposing and crystallizing, and refined potassium mother liquor, a second-stage crystallization mother liquor and fine crystal dissolving mother liquor which are generated in the subsequent process are added at the same time, so that first-stage crystallizer underflow slurry and first-stage crystallizer overflow are obtained, the first-stage crystallizer underflow slurry is delivered into the second-stage crystallizer, and meanwhile, the second-stage fine crystal dissolving mother liquor is added, and the undegraded carnallite is continuously decomposed and crystallized, so that second-stage crystallizer underflow slurry and second-stage crystallizer overflow are obtained;
fine-grain dissolution: and (3) carrying out the following treatment on the overflow of the primary crystallizer and the overflow of the secondary crystallizer obtained in the step (a):
(1) the overflow of the first-stage crystallizer flows into a first-stage overflow thickener, and solid fine crystals contained in the overflow are settled and concentrated in the thickener to obtain underflow slurry of the first-stage overflow thickener and first-stage crystallization mother liquor; and sending the underflow slurry of the first-stage overflow thickener into a first-stage fine-grain dissolution tank, adding a proper amount of fresh water to dissolve solid fine grains into a liquid phase, and then returning all the first-stage fine-grain dissolution mother liquor into the first-stage crystallizer.
(2) The overflow of the second-stage crystallizer automatically flows into a second-stage overflow thickener, and solid fine crystals contained in the overflow are settled and concentrated in the thickener to obtain underflow slurry and second-stage crystallization mother liquor of the second-stage overflow thickener; and then the underflow slurry of the two-stage overflow thickener is sent into a two-stage fine crystal dissolving tank, a proper amount of fresh water is added to dissolve solid fine crystals into a liquid phase, and then the two-stage fine crystal dissolving mother liquor is completely returned into the two-stage crystallizer.
(3) All the primary crystallization mother liquor obtained in the step (1) is used for grinding and pulping;
(4) returning all the second-stage crystallization mother liquor obtained in the step (2) to the first-stage crystallizer;
floatation: sending the underflow slurry of the second-stage crystallizer obtained in the step (IV) into flotation equipment for flotation, adding a flotation reagent, carrying out primary roughing, primary scavenging and secondary to tertiary concentration to obtain concentrate foam and tail salt slurry, wherein the concentrate foam is filtered to obtain coarse potassium, the tail salt slurry is pumped into a tail salt pond or filtered to obtain tail salt, and the tail salt is sent to a tail salt storage yard for temporary storage; the filtrate obtained after the concentrate and the tail salt are filtered is used for adjusting the concentration of flotation operation;
washing: adding the crude potassium obtained in the step (a) into a washing tank, adding a proper amount of fresh water at the same time, performing repulping washing, filtering the washed slurry to obtain refined potassium and refined potassium filtrate, wherein the refined potassium filtrate, namely refined potassium mother liquor, returns to a first-stage crystallizer;
drying: drying the refined potassium obtained in the step (a), and obtaining a potassium chloride product.
In the technical scheme of the process, the further preferable technical scheme is as follows:
1. step II, the size mixing brine is a section of crystallization mother liquor, and the fine crusher adopts a cage fine crusher or a rod mill.
2. Step III, the desliming equipment is selected from a hydrocyclone, a desliming bucket or a conical hydraulic classifier;
3. step four, the decomposing crystallizer is a DTB type crystallizer;
4. the total addition amount of fresh water (namely the sum of the fresh water addition amount of the first section of fine grain dissolution tank and the fresh water addition amount of the second section of fine grain dissolution tank) is 105% -115% of the theoretical decomposition water amount of carnallite raw ore (the fresh water amount for just decomposing carnallite is calculated according to a quaternary water salt system phase diagram), wherein the fresh water addition amount of the first section of fine grain dissolution tank is 40% -60% of the total fresh water addition amount;
5. the addition amount of the washing fresh water is 110-120% of the theoretical water addition amount (theoretical value calculated according to the composition of the washing raw materials and the phase diagram data of the quaternary water salt system), and the washing time is 30-60 min.
Compared with the prior art, the process has the following beneficial effects:
(1) the invention adopts a mechanical desliming process, so that the influence of mineral mud on the separation effect of flotation operation and the quality of potassium chloride products is avoided;
(2) the invention adopts a decomposition crystallization process with two sections of crystallizers connected in series, which not only ensures complete decomposition of carnallite and greatly reduces the fresh water addition amount of the decomposition crystallizer, but also ensures that the potassium chloride content in the externally discharged first section of decomposition mother liquor (namely crystallization mother liquor) is far lower than that in the decomposition mother liquor in the conventional decomposition process, thereby improving the process recovery rate of the decomposition crystallization process;
(3) according to the invention, the overflow liquid of the first-stage crystallizer and the overflow liquid of the second-stage crystallizer are subjected to a fine crystal dissolving process, so that potassium chloride fine crystals contained in the overflow liquid of the crystallizer are recovered, the granularity of the product is increased, and the energy consumption of the subsequent dehydration and drying process is greatly reduced;
(4) the potassium chloride produced by the process has high product quality, low production cost and high process recovery rate, and is easy for large-scale industrialized implementation. The KCl content of the prepared potassium chloride product is more than or equal to 95 percent, and the KCl process recovery rate is more than or equal to 72 percent.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further illustrated below with reference to examples of implementation.
Example 1 referring to fig. 1, a process experiment 1 for producing potassium chloride using virgin carnallite ore:
the method comprises the steps of mixing carnallite ore (containing KCl 16.1%, naCl 45.3% and MgCl 2 18.1%, water insoluble 1.2%) to a particle size below 25 mm.
And (3) mixing a section of crystallization mother liquor generated in the follow-up procedure of the crushed carnallite ore, and then sending the mixture to a cage type fine crusher for wet crushing, so that the carnallite ore is crushed to have the granularity of 2.0mm.
Thirdly, the finely crushed ore pulp is sent to a hydrocyclone for desliming, and insoluble ore slime is removed.
And (3) conveying the desliming materials to a carnallite decomposition crystallization device, wherein the decomposition crystallization device is formed by connecting a first-stage crystallizer and a second-stage crystallizer in series, slurry is firstly added into the first-stage crystallizer, and refined potassium mother liquor, a second-stage crystallization mother liquor and a first-stage fine crystal dissolution mother liquor which are generated in the subsequent procedures are simultaneously added, and carnallite is decomposed and crystallized in the crystallizer to obtain first-stage crystallizer underflow slurry and first-stage crystallizer overflow, the first-stage crystallizer underflow slurry is conveyed into the second-stage crystallizer, and the undegraded carnallite is continuously decomposed and crystallized to obtain second-stage crystallizer underflow slurry and second-stage crystallizer overflow.
Fifthly, flowing overflow of the first-stage crystallizer into a first-stage overflow thickener, clarifying and concentrating by the thickener to obtain underflow slurry of the first-stage overflow thickener and a first-stage crystallization mother liquor, feeding the underflow slurry of the first-stage overflow thickener into a first-stage fine-grain dissolving tank, adding fresh water according to 40% of total carnallite decomposition water quantity, dissolving solid fine grains, and returning to the first-stage crystallizer; the overflow of the second-stage crystallizer flows into a second-stage overflow thickener from the overflow of the second-stage crystallizer, the underflow slurry of the second-stage overflow thickener and the second-stage crystallization mother liquor are obtained after clarification and concentration by the thickener, the underflow slurry of the second-stage overflow thickener is sent into a second-stage fine crystal dissolving tank, fresh water is added according to 60 percent of the total decomposing water quantity of carnallite, solid fine crystals are dissolved and then returned to the second-stage crystallizer, the second-stage crystallization mother liquor is returned to the first-stage crystallizer,
the total carnallite decomposition water quantity is 105% of the carnallite theoretical decomposition water quantity calculated according to the composition of the raw carnallite ore and the phase diagram of the quaternary water salt system.
Sending the underflow slurry of the second-stage crystallizer into a flotation device for flotation, adding a flotation reagent, carrying out primary roughing, primary scavenging and tertiary concentration to obtain concentrate foam and tail salt slurry, wherein the concentrate foam is filtered to obtain coarse potassium, the tail salt slurry is filtered to obtain tail salt, and the tail salt is sent to a tail salt storage yard for temporary storage; the filtrate after concentrate and tail salt filtration is used to adjust the flotation working concentration.
And adding the crude potassium into a washing tank, adding fresh water according to 115% of the theoretical water adding amount calculated by a quaternary water salt system, performing repulping washing for 40min, filtering the washed slurry to obtain refined potassium and refined potassium filtrate, and returning the filtrate, namely refined potassium mother liquor, to the first-stage crystallizer.
And drying the obtained refined potassium to obtain a potassium chloride product, wherein the maximum particles of the potassium chloride can reach 0.42mm, the average particle size can reach 0.26mm, the KCl content is 95.5%, and the recovery rate is 74%.
Example 2, process experiment 2 for producing potassium chloride using virgin carnallite ore:
the method comprises the steps of mixing carnallite ore (containing KCl 15.1%, naCl 41.5% and MgCl) 2 19.6%, water insoluble 0.9%) to below 25 mm.
And (3) mixing the primary crystallization mother liquor generated in the subsequent process of coarse crushing of the crude ore to 50% concentration, and delivering the primary crystallization mother liquor to a rod mill for ore grinding, wherein the primary carnallite ore is ground to-2.0 mm.
Thirdly, the ore pulp after ore grinding is sent to a conical hydraulic classifier for desliming, and insoluble ore mud is removed.
And (3) conveying the desliming materials to a carnallite decomposition crystallization device, wherein the decomposition crystallization device is formed by connecting a first-stage crystallizer and a second-stage crystallizer in series, slurry is firstly added into the first-stage crystallizer, and refined potassium mother liquor, a second-stage crystallization mother liquor and a first-stage fine crystal dissolution mother liquor which are generated in the subsequent procedures are simultaneously added, and carnallite is decomposed and crystallized in the crystallizer to obtain first-stage crystallizer underflow slurry and first-stage crystallizer overflow, the first-stage crystallizer underflow slurry is conveyed into the second-stage crystallizer, and the undegraded carnallite is continuously decomposed and crystallized to obtain second-stage crystallizer underflow slurry and second-stage crystallizer overflow.
Fifthly, flowing overflow of the first-stage crystallizer into a first-stage overflow thickener, clarifying and concentrating by the thickener to obtain underflow slurry of the first-stage overflow thickener and a first-stage crystallization mother liquor, feeding the underflow slurry of the first-stage overflow thickener into a first-stage fine-grain dissolving tank, adding fresh water according to 50% of total carnallite decomposition water quantity, dissolving solid fine grains, and returning to the first-stage crystallizer; the overflow of the second-stage crystallizer flows into a second-stage overflow thickener from the overflow of the second-stage crystallizer, the underflow slurry of the second-stage overflow thickener and the second-stage crystallization mother liquor are obtained after clarification and concentration by the thickener, the underflow slurry of the second-stage overflow thickener is sent into a second-stage fine crystal dissolving tank, fresh water is added according to 50 percent of the total decomposing water quantity of carnallite, solid fine crystals are dissolved and then returned to the second-stage crystallizer, the second-stage crystallization mother liquor is returned to the first-stage crystallizer,
the total carnallite decomposition water quantity is 115% of the carnallite theoretical decomposition water quantity calculated according to the carnallite raw ore composition and the quaternary water salt system phase diagram.
Sending underflow slurry of the second-stage crystallizer into a flotation device for flotation, adding a flotation reagent, performing primary roughing, primary scavenging and secondary concentration to obtain concentrate foam and tail salt slurry, filtering the concentrate foam to obtain coarse potassium, and pumping the tail salt slurry into a tail salt pond for temporary storage; the filtrate after concentrate filtration and the mother liquor of the tail salt pond are used for adjusting the concentration of flotation operation.
And adding the crude potassium into a washing tank, adding fresh water according to 110% of the theoretical water adding amount calculated by a quaternary water salt system, performing repulping washing for 30min, filtering the washed slurry to obtain refined potassium and refined potassium filtrate, and returning the filtrate, namely refined potassium mother liquor, to the first-stage crystallizer.
The potassium chloride product is obtained after drying the obtained refined potassium, the whiteness of the potassium chloride is higher, the average particle size reaches 0.3mm, the KCl content is 95.3%, and the recovery rate is 72%.
Example 3, process experiment 3 for producing potassium chloride using virgin carnallite ore:
the method comprises the steps of mixing carnallite ore (containing KCl 18.4%, naCl 29.3% and MgCl) 2 23.3%, water insoluble 0.5%) to below 25 mm.
And (3) mixing the first-stage crystallization mother liquor generated in the subsequent process of the crushed carnallite ore to 70% concentration, and delivering the mixed solution to a rod mill for ore grinding, wherein the carnallite ore is ground to-2.0 mm.
And thirdly, conveying the ore pulp after ore grinding to a desliming bucket for desliming, and removing insoluble ore slimes.
And (3) conveying the desliming materials to a carnallite decomposition crystallization device, wherein the decomposition crystallization device is formed by connecting a first-stage crystallizer and a second-stage crystallizer in series, slurry is firstly added into the first-stage crystallizer, and refined potassium mother liquor, a second-stage crystallization mother liquor and a first-stage fine crystal dissolution mother liquor which are generated in the subsequent procedures are simultaneously added, and carnallite is decomposed and crystallized in the crystallizer to obtain first-stage crystallizer underflow slurry and first-stage crystallizer overflow, the first-stage crystallizer underflow slurry is conveyed into the second-stage crystallizer, and the undegraded carnallite is continuously decomposed and crystallized to obtain second-stage crystallizer underflow slurry and second-stage crystallizer overflow.
Fifthly, flowing overflow of the first-stage crystallizer into a first-stage overflow thickener, clarifying and concentrating by the thickener to obtain underflow slurry of the first-stage overflow thickener and a first-stage crystallization mother liquor, feeding the underflow slurry of the first-stage overflow thickener into a first-stage fine-grain dissolving tank, adding fresh water according to 60% of total carnallite decomposition water quantity, dissolving solid fine grains, and returning to the first-stage crystallizer; the overflow of the second-stage crystallizer flows into a second-stage overflow thickener from the overflow of the second-stage crystallizer, the underflow slurry of the second-stage overflow thickener and the second-stage crystallization mother liquor are obtained after clarification and concentration by the thickener, the underflow slurry of the second-stage overflow thickener is sent into a second-stage fine crystal dissolving tank, fresh water is added according to 40 percent of the total decomposing water quantity of carnallite, solid fine crystals are dissolved and then returned to the second-stage crystallizer, the second-stage crystallization mother liquor is returned to the first-stage crystallizer,
the total carnallite decomposition water quantity is 115% of the carnallite decomposition water quantity calculated according to the carnallite raw ore composition and the quaternary water salt system phase diagram.
Sending the underflow slurry of the second-stage crystallizer into a flotation device for flotation, adding a flotation reagent, carrying out primary roughing, primary scavenging and secondary concentration to obtain concentrate foam and tail salt slurry, wherein the concentrate foam is filtered to obtain coarse potassium, the tail salt slurry is filtered to obtain tail salt, and the tail salt is sent to a tail salt storage yard for temporary storage; the filtrate after concentrate and tail salt filtration is used to adjust the flotation working concentration.
Adding coarse potassium into a washing tank, adding fresh water accounting for 120% of the theoretical water adding amount calculated according to a quaternary water salt system, performing repulping washing for 60min, filtering the washed slurry to obtain refined potassium and refined potassium filtrate, and returning the filtrate, namely refined potassium mother liquor, to a first-stage crystallizer.
The potassium chloride product is prepared after the obtained refined potassium is dried, the whiteness of the potassium chloride is higher, the average particle size is 0.28mm, the KCl content is 96.2%, and the recovery rate of the KCl process is 75%.
Claims (6)
1. A process for producing potassium chloride by using primary carnallite ore, which is characterized by comprising the following steps:
coarse crushing: crushing solid carnallite ore to a granularity below 25 mm;
finely divided: adding the materials obtained in the step (A) into size mixing brine, and then sending the slurry into a fine crusher for wet crushing, wherein the granularity of the finely crushed ore is less than or equal to 2mm;
desliming: feeding the materials obtained in the step (II) into desliming equipment to desliming, and removing insoluble mineral mud;
and (3) crystallizing: delivering the desliming material obtained in the step III to a carnallite decomposing and crystallizing device, wherein the decomposing and crystallizing device is formed by connecting a first-stage crystallizer and a second-stage crystallizer in series, carnallite slurry is firstly added into the first-stage crystallizer for decomposing and crystallizing, and refined potassium mother liquor, a second-stage crystallization mother liquor and fine crystal dissolving mother liquor which are generated in the subsequent process are added at the same time, so that first-stage crystallizer underflow slurry and first-stage crystallizer overflow are obtained, the first-stage crystallizer underflow slurry is delivered into the second-stage crystallizer, and meanwhile, the second-stage fine crystal dissolving mother liquor is added, and the undegraded carnallite is continuously decomposed and crystallized, so that second-stage crystallizer underflow slurry and second-stage crystallizer overflow are obtained;
fine-grain dissolution: and (3) carrying out the following treatment on the overflow of the primary crystallizer and the overflow of the secondary crystallizer obtained in the step (a):
(1) the overflow of the first-stage crystallizer flows into a first-stage overflow thickener, and solid fine crystals contained in the overflow are settled and concentrated in the thickener to obtain underflow slurry of the first-stage overflow thickener and first-stage crystallization mother liquor; sending the underflow slurry of the first-stage overflow thickener into a fine-grain dissolution tank, adding a proper amount of fresh water to dissolve solid fine grains into a liquid phase, and returning all the first-stage fine-grain dissolution mother liquor into the first-stage crystallizer;
(2) the overflow of the second-stage crystallizer automatically flows into a second-stage overflow thickener, and solid fine crystals contained in the overflow are settled and concentrated in the thickener to obtain underflow slurry and second-stage crystallization mother liquor of the second-stage overflow thickener; then sending the underflow slurry of the two-stage overflow thickener into a fine-grain dissolving tank, adding a proper amount of fresh water to dissolve solid fine grains into a liquid phase, and then returning the two-stage fine-grain dissolving mother liquor to the two-stage crystallizer;
(3) all the primary crystallization mother liquor obtained in the step (1) is used for grinding and pulping;
(4) returning all the second-stage crystallization mother liquor obtained in the step (2) to the first-stage crystallizer;
floatation: sending the underflow slurry of the second-stage crystallizer obtained in the step (IV) to flotation equipment for flotation, adding a flotation reagent, carrying out primary roughing, primary scavenging and secondary to tertiary concentration to obtain concentrate foam and tail salt slurry, wherein the concentrate foam automatically flows to a filtering system, crude potassium is obtained through filtering, the tail salt slurry is pumped to a tail salt pond or filtered to obtain tail salt, and the tail salt is conveyed to a tail salt storage yard for temporary storage; the filtrate obtained after the concentrate and the tail salt are filtered is used for adjusting the concentration of flotation operation;
washing: adding the crude potassium obtained in the step (a) into a washing tank, adding a proper amount of fresh water at the same time, performing repulping washing, filtering the washed slurry to obtain refined potassium, and returning the filtered filtrate, namely refined potassium mother liquor, to a first-stage crystallizer;
drying: drying the refined potassium obtained in the step (a), and obtaining a potassium chloride product.
2. The process of claim 1, wherein the size-mixed brine is a section of crystallization mother liquor, and the fine crusher is a cage fine crusher or a rod mill.
3. The process of claim 1, wherein the desliming device of step (a) is selected from the group consisting of a hydrocyclone, desliming hopper, and conical hydraulic classifier.
4. The process of claim 1, wherein the crystallizer of step (a) is a DTB type crystallizer.
5. The process according to claim 1, wherein the total addition of fresh water in the step (i.e. the sum of the fresh water addition of the first section of fine grain dissolution tank and the fresh water addition of the second section of fine grain dissolution tank) is 105% -115% of the theoretical decomposition water amount of carnallite raw ore, namely the fresh water amount for just decomposing carnallite is calculated according to a quaternary salt system phase diagram, and the fresh water addition of the first section of fine grain dissolution tank is 40% -60% of the total fresh water addition.
6. The process according to claim 1, wherein the addition of the washing fresh water in the step (a) is 110-120% of the theoretical addition, i.e. the theoretical value calculated according to the composition of the washing raw materials and the phase diagram data of the quaternary water salt system, and the washing time is 30-60 min.
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