WO2014161248A1 - System and process for preparing large-particle potassium chloride by cold-decomposition crystallization and flotation method with high-sodium potassic salt ore - Google Patents
System and process for preparing large-particle potassium chloride by cold-decomposition crystallization and flotation method with high-sodium potassic salt ore Download PDFInfo
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- WO2014161248A1 WO2014161248A1 PCT/CN2013/079269 CN2013079269W WO2014161248A1 WO 2014161248 A1 WO2014161248 A1 WO 2014161248A1 CN 2013079269 W CN2013079269 W CN 2013079269W WO 2014161248 A1 WO2014161248 A1 WO 2014161248A1
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- Prior art keywords
- potassium chloride
- crystallizer
- cold
- cold decomposition
- sodium
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 title claims abstract description 152
- 239000001103 potassium chloride Substances 0.000 title claims abstract description 76
- 235000011164 potassium chloride Nutrition 0.000 title claims abstract description 76
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 75
- 239000002245 particle Substances 0.000 title claims abstract description 38
- 238000005188 flotation Methods 0.000 title claims abstract description 29
- 238000002425 crystallisation Methods 0.000 title claims abstract description 26
- 230000008025 crystallization Effects 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000011734 sodium Substances 0.000 title abstract description 9
- 229910052708 sodium Inorganic materials 0.000 title abstract description 9
- 150000003839 salts Chemical class 0.000 title abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000013505 freshwater Substances 0.000 claims abstract description 14
- 238000003860 storage Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 52
- 239000000047 product Substances 0.000 claims description 44
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 34
- 239000011780 sodium chloride Substances 0.000 claims description 17
- 230000008030 elimination Effects 0.000 claims description 15
- 238000003379 elimination reaction Methods 0.000 claims description 15
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 6
- 239000012267 brine Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 239000012530 fluid Substances 0.000 abstract description 2
- 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 description 12
- 239000002994 raw material Substances 0.000 description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 235000015320 potassium carbonate Nutrition 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910001577 potassium mineral Inorganic materials 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- DOJFLZVCYRFAJO-UHFFFAOYSA-N [K].[Na].[Sr] Chemical compound [K].[Na].[Sr] DOJFLZVCYRFAJO-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
Definitions
- the invention belongs to the field of chemical industry, and relates to a process for controlling the crystal size of a product in a potassium fertilizer production process, specifically a potassium salt mine having a high sodium chloride content as a raw material, and a crystal of potassium chloride in a potassium salt mine is controlled by a cold decomposition crystallization technique.
- the particle size, and then the flotation method is used to separate the cold crystal mixed product to obtain the production process and equipment of the large particle potassium chloride product.
- Potassium chloride is one of the important agricultural potashes. According to IFA statistics, the demand for potash in the world in 2011 was 36.44 million tons (in K 2 0), and the demand for potash increased at a rate of about 1 million tons per year. China is a big agricultural country and the second largest country for potash consumption. Currently, the amount of potassium needed is 10 million tons per year (in real terms), of which about 5 million tons need to enter ⁇ .
- the potassium salt mines in Southeast Asia are mainly distributed in Thailand and Laos.
- the potassium resources here are mainly carnallite and potash salts, and are mainly carnallite mines.
- the potassium ore has a sodium chloride content of up to 50% by mass, while sodium Ions have a significant effect on the particle size of the potassium chloride crystal product.
- the company uses potassium high-sodium ore as raw material to produce potassium chloride as a direct decomposition method, and does not control the particle size of potassium chloride products.
- the potassium chloride product has a small particle size, mostly powdery, and operates in the centrifugal separation process and the drying process. The cost is high, and the post-order granulation technology is often used to form the final product.
- a method and a device for producing potassium chloride from carnallite uses a carnallite slurry as a raw material, and thickens and fractionates sodium chloride and reverse flotation to obtain coarse fine haw.
- the filter cake is then subjected to crystallization to obtain crude potassium base, which is finally purified to obtain potassium chloride crystals.
- the method firstly pretreats the sodium chloride in the raw material to become a raw material containing a lower sodium concentration, and then produces potassium chloride, and the research object is not directed to the high sodium potassium mineral salt.
- a method for extracting potassium chloride from a mixed mineral of potassium salt and carnallite (CN1259486), which is obtained by crushing a mixed salt of potassium salt and carnallite recovered in a salt field, and then adding a saturated brine to grind, and then Flotation, filtration and drying to obtain potassium chloride solid, the key is to use octadecylamine as a scavenger in the flotation process, and carboxymethyl cellulose as an inhibitor to increase the recovery rate of potassium chloride.
- the raw materials are not high sodium potassium minerals, but also how to improve potassium chloride products. The particle size has not been explored.
- the invention will first prepare low sodium carnallite by reverse flotation, followed by fresh water decomposition, crystallization, centrifugal filtration
- the KC1 is dried, and the secondary crystal is dissolved by microfiltration to obtain a larger particle KC1.
- the study object was low sodium carnallite instead of high sodium carnallite.
- the object of the present invention is to overcome the deficiencies of the prior art, and provide a system and a process for preparing large-particle potassium chloride by cold decomposition crystallization and flotation of high sodium potassium salt ore, that is, using high sodium potassium salt ore as raw material.
- a method for obtaining large-particle potassium chloride products by cold decomposition crystallization process control and flotation separation, and at the same time, according to the process parameters, a crystallizer structure and operating parameters for realizing the particle size control of the potassium chloride product are proposed.
- Cold decomposition crystallization and flotation method of high-sodium potassium salt ore to prepare large-particle potassium chloride system which is formed by feeding control system, cold decomposition crystallizer, fine crystal elimination tank and fresh water storage tank in sequence, in cold A stirring paddle is disposed in the decomposition crystallizer, and a circulation pump for conveying the circulating liquid is further installed between the fine crystal eliminating tank and the cold decomposition crystallizer, and a water pump is installed in the supply line of the fresh water storage tank.
- the cold decomposition crystallizer comprises an inner guide tube and an outer guide tube, a stirring paddle, a stirring motor, an overflow tank, a top feed port, a top overflow port, a bottom discharge port, and an ⁇ -type structure at the bottom thereof.
- the agitating paddle of the cold decomposition crystallizer is a single-layer blade structure or a double-layer blade structure, the agitating blade is a flat blade type or a propulsion type, and the overflow weir plate in the overflow groove is a tooth-shaped structure.
- the high-sodium potassium salt mine with a sodium chloride mass percentage of 30% ⁇ 60% is sieved through a standard sieve with a mesh diameter of lmm ⁇ 10mm, and the sieved material is used as a feed and a continuous screw feeding system is adopted.
- the feed rate of high sodium potassium salt mine is lkg/h ⁇ 500t/h
- the mass concentration of MgCl 2 in the circulating liquid is 15% -30%
- the residence time in the cold decomposition crystallizer is Lh ⁇ 5h
- the operating temperature is 20 °C ⁇ 40 °C
- the stirring speed of the straight leaf type or propeller type stirring paddle is 20 rpm ⁇ 700 rpm
- the large particle potassium chloride product is obtained in the cold decomposition crystallizer
- the potassium chloride fine crystal product obtained at the top of the cold decomposition crystallizer in the step (1) enters the fine crystal elimination tank in the form of mother liquor overflow, and the fresh water having a flow rate of 0.15 IJh to 150 m 3 /h is continuously added to the fine crystal.
- the can is eliminated to dissolve the fine crystal of potassium chloride in the tank, and after dissolving the potassium chloride, the fine crystal eliminates the liquid in the tank as a circulating liquid, and the circulating liquid is continuously returned to the cold decomposition crystallizer by the circulation pump, and the circulating liquid in the cold decomposition crystallizer
- the rate of addition is 1.3 kg / h ⁇ 2500 t / h ;
- the product is sieved through a 10 mesh to 50 mesh Taylor standard sieve in the same sieve composition as the decomposition liquid of the cold decomposition crystallizer.
- the sieve liquid is the same as the mother liquid in the cold decomposition crystallizer, and the sieved material is filtered by suction filtration.
- the cake is slurried in a flotation machine and sieved in absolute ethanol through a rough selection and twice selected filter cake to obtain a potassium chloride product.
- the sieving liquid in the step (3) is the same brine or absolute ethanol as the mother liquid in the cold decomposition crystallizer.
- the present invention is directed to a process for producing potassium chloride by using a high-sodium potassium salt ore as a raw material, and a process for separating a crystalline underflow product by a particle size-flotation method of a potassium chloride product by cold decomposition crystallization, thereby obtaining a large-particle potassium chloride crystal product, It is of great significance to further optimize the equipment selection of the engineering design of the concentrator, improve the reliability and stability of the operation of the equipment, and reduce the operating cost of the equipment. At the same time, it saves the operating cost of the centrifugal separation operation and the drying process in the production process, and reduces the overall cost of the product.
- the invention overcomes the shortcomings of the direct decomposition of high-sodium potassium salt ore to obtain a small potassium chloride product, high operating cost of the centrifugal separation process and the drying process, and the use of the subsequent granulation technology to form the final product.
- the invention produces potassium chloride by setting the process and parameter control conditions for the high sodium salt mine of sodium chloride (NaCl) content of 30% ⁇ 60%, realizing the use of high sodium potassium salt ore as raw material.
- the particle size of the potassium chloride crystal product is controlled, and the obtained product has an average particle size of 0.15 mm to 0.35 mm, which improves the market competitiveness of producing potassium chloride products by using high sodium potassium salt ore as raw material.
- the economic benefits are very significant and the market prospect is broad.
- Figure 1 is a process flow diagram of the present invention
- FIG. 2 is a schematic structural view of a system of the present invention
- Figure 3 is a front elevational view showing the structure of the cold decomposition crystallizer of the present invention.
- Fig. 4 is a schematic view showing the structure of the A-A direction of Fig. 3.
- a system for preparing large-particle potassium chloride by cold decomposition crystallization and flotation of high-sodium potassium salt ore see Figures 2, 3, and 4, the whole system is eliminated by feed control system 1, cold decomposition crystallizer 3, fine crystal
- the tank 6 and the fresh water storage tank 8 are connected in sequence, and the cold decomposition crystallizer is connected with the constant temperature water bath 2, and the cold decomposition crystallizer can be provided with a jacket to keep the liquid in the crystallizer at the set operating temperature, in the jacket.
- the medium may be water, and the temperature of the water entering the crystallizer jacket may be heated and controlled by a constant temperature water bath or steam, and a stirring paddle 4 is disposed in the cold decomposition crystallizer.
- a circulation pump 5 is also installed between the fine crystal elimination tank and the cold decomposition crystallizer, and a water pump 7 is installed in the supply line of the fresh water storage tank.
- the machine, the overflow tank, the top overflow port, and the bottom discharge port have an ⁇ -shaped structure at the bottom.
- the agitating paddle is a single-layer blade structure or a double-layer blade structure, and the agitating paddle is a flat blade type or a propulsion type;
- the material used for the cold decomposition crystallizer is cast iron, alloy steel, carbon steel or stainless steel, overflow in the overflow tank
- the flow board is a toothed structure.
- the high-sodium potassium salt mine with a sodium chloride mass percentage of 29.84% is sieved through a standard sieve having a mesh diameter of 4 mm, and the sieved material is fed as a feed and continuously added to the cold decomposition crystallization by a continuous screw feeding system.
- the feed rate of high sodium potassium salt mine is 2.38kg / h
- the mass concentration of MgCl 2 in the circulating fluid is 23%
- the residence time of the crystallizer is 3.55 hours
- the operating temperature is 25 ° C
- the propulsion stirring paddle The stirring speed was 400 rpm, and a large particle potassium chloride product was obtained in the crystallizer.
- the potassium chloride fine crystal product obtained at the top of the crystallizer in the step (1) enters the fine crystal elimination tank in the form of mother liquor overflow, and the fresh water having a flow rate of 0.65 IJh is continuously added to the fine crystal elimination tank to dissolve the inside of the tank.
- the fine crystal of potassium chloride dissolves the potassium chloride and dissolves the liquid in the tank as a circulating liquid.
- the circulating liquid is continuously returned to the crystallizer by the circulating pump, and the circulation rate of the circulating liquid in the crystallizer is 5.87 kg/h.
- the average particle diameter of KC1 was 0.18 mm, and the yield of KC1 was 58%.
- the high-sodium potassium salt mine with a sodium chloride mass percentage of 42.50% is sieved through a standard sieve having a mesh diameter of 6 mm, and the sieved material is fed as a feed and continuously added to the cold decomposition crystallizer by a continuous screw feeding system.
- the feed rate of high sodium potassium salt mine is 3.95kg / h
- the mass concentration of MgCl 2 in the circulating liquid is 25%
- the residence time of the crystallizer is 2.26 hours
- the operating temperature is 27 ° C
- the straight stirring paddle The stirring speed was 600 rpm, and a large particle potassium chloride product was obtained in the crystallizer.
- the potassium chloride fine crystal product obtained at the top of the crystallizer in the step (1) enters the fine crystal elimination tank in the form of mother liquor overflow, and the fresh water having a flow rate of 0.23 IJh is continuously added to the fine crystal elimination tank to dissolve the inside of the tank.
- the fine crystal of potassium chloride dissolves the potassium chloride and dissolves the liquid in the tank as a circulating liquid.
- the circulating liquid is continuously returned to the crystallizer by the circulating pump, and the circulation rate of the circulating liquid in the crystallizer is 5.87 kg/h.
- the average particle diameter of KC1 was 0.16 mm, and the yield of KC1 was 51%.
- the high-sodium potassium salt mine with a sodium chloride mass percentage of 39.06% is sieved through a standard sieve having a mesh diameter of 8 mm, and the sieved material is fed as a feed and continuously added to the cold decomposition crystallization by a continuous screw feeding system.
- the feed rate of high sodium potassium salt mine is 2.66kg / h
- the mass concentration of MgCl 2 in the circulating liquid is 24%
- the residence time of the crystallizer is 3.50 hours
- the operating temperature is 35 ° C
- the propulsion stirring paddle The stirring speed was 400 rpm, and a large particle potassium chloride product was obtained in the crystallizer.
- the potassium chloride fine crystal product obtained at the top of the crystallizer in the step (1) enters the fine crystal elimination tank in the form of mother liquor overflow, and the fresh water having a flow rate of 0.49IJh is continuously added to the fine crystal elimination tank to dissolve the inside of the tank.
- the fine crystal of potassium chloride dissolves the potassium chloride and dissolves the liquid in the tank as a circulating liquid.
- the circulating liquid is continuously returned to the crystallizer by the circulating pump, and the circulation rate of the circulating liquid in the crystallizer is 5.03 kg/h.
- the average particle diameter of KC1 was 0.20 mm, and the yield of KC1 was 56%.
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Abstract
Provided is a system for preparing large-particle potassium chloride by cold-decomposition crystallization and a flotation method with high-sodium potassic salt ore. The system is formed by sequentially connecting a feeding control system, a cold-decomposition crystallizer, a fine crystal removing tank, and a fresh water storage tank, a stirring paddle being provided in the cold-decomposition crystallizer, a circulating pump for delivering circulation fluid being mounted between the fine crystal removing tank and the cold-decomposition crystallizer, and a water pump being mounted on a supply pipe of the fresh water storage tank. Also provided is a process for preparing large-particle potassium chloride by cold-decomposition crystallization and a flotation method with high-sodium potassic salt ore.
Description
髙钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的系统及工艺 技术领域 System and process for preparing large-particle potassium chloride by cold decomposition crystallization and flotation method of strontium sodium potassium salt ore
本发明属于化工领域， 涉及钾肥生产过程中产品晶体粒度的控制工艺， 具体地说是以 高氯化钠含量的钾盐矿为原料， 采用冷分解结晶技术控制钾盐矿中氯化钾的晶体粒度， 进 而采用浮选方法分离冷结晶混合产品获得大颗粒氯化钾产品的生产工艺及设备。 The invention belongs to the field of chemical industry, and relates to a process for controlling the crystal size of a product in a potassium fertilizer production process, specifically a potassium salt mine having a high sodium chloride content as a raw material, and a crystal of potassium chloride in a potassium salt mine is controlled by a cold decomposition crystallization technique. The particle size, and then the flotation method is used to separate the cold crystal mixed product to obtain the production process and equipment of the large particle potassium chloride product.
背景技术 Background technique
氯化钾是重要的农业钾肥之一。 IFA统计资料表明， 2011年世界钾盐的需求量为 3644 万吨 （以 K20计）， 钾肥需求量以每年约 100万吨的速率增长。 中国是农业大国， 也是钾 肥消费第二大国， 目前每年需要的钾量为 1000万吨 （以实物计）， 其中约 500万吨需要进 π。 Potassium chloride is one of the important agricultural potashes. According to IFA statistics, the demand for potash in the world in 2011 was 36.44 million tons (in K 2 0), and the demand for potash increased at a rate of about 1 million tons per year. China is a big agricultural country and the second largest country for potash consumption. Currently, the amount of potassium needed is 10 million tons per year (in real terms), of which about 5 million tons need to enter π.
东南亚的钾盐矿主要分布于泰国和老挝， 这里的钾资源主要是光卤石和钾石盐， 且以 光卤石矿为主， 钾矿石的氯化钠质量百分含量高达 50%， 而钠离子对氯化钾晶体产品粒度 有明显影响。 目前， 企业以高钠钾矿为原料生产氯化钾为直接分解方法， 没有控制氯化钾 产品的粒度， 氯化钾产品粒度较小， 多为粉状， 在离心分离过程和干燥过程的运行成本高， 且多采用后序造粒技术形成最终产品。 因此， 开发针对高钠钾盐矿中光卤石冷分解过程制 备氯化钾结晶工艺， 并采用浮选的方法分离结晶后氯化钠与氯化钾混合物料， 获得平均粒 度大的氯化钾晶体产品， 这不仅降低运行成本， 同时必将大幅度提升以高钠钾盐矿为原料 的氯化钾产品的市场竞争力， 经济效益可观、 市场前景广阔。 The potassium salt mines in Southeast Asia are mainly distributed in Thailand and Laos. The potassium resources here are mainly carnallite and potash salts, and are mainly carnallite mines. The potassium ore has a sodium chloride content of up to 50% by mass, while sodium Ions have a significant effect on the particle size of the potassium chloride crystal product. At present, the company uses potassium high-sodium ore as raw material to produce potassium chloride as a direct decomposition method, and does not control the particle size of potassium chloride products. The potassium chloride product has a small particle size, mostly powdery, and operates in the centrifugal separation process and the drying process. The cost is high, and the post-order granulation technology is often used to form the final product. Therefore, a crystallization process for preparing potassium chloride for the cold decomposition process of carnallite in high-sodium potassium salt ore was developed, and a mixture of sodium chloride and potassium chloride was separated by crystallization to obtain a potassium chloride having a large average particle size. Crystal products, which not only reduce operating costs, but also greatly enhance the market competitiveness of potassium chloride products with high sodium and potassium salt ore as raw materials, with considerable economic benefits and broad market prospects.
目前， 国内尚无大规模针对以高钠钾盐矿为原料， 结晶生产大粒径氯化钾的实例及相 关经验。 At present, there is no large-scale example and related experience in the production of large-diameter potassium chloride by high-sodium potassium salt ore as raw material.
通过检索， 发现如下三篇与本发明专利申请相关的公开专利文献： Through the search, the following three published patent documents related to the patent application of the present invention were found:
1、 由光卤石生产氯化钾的方法和设备 （CN1260323), 该发明以光卤石浆料为原料， 经增稠、分级除氯化钠、反向浮选的方法获得粗细光卤石滤饼， 而后经结晶法获得粗钾碱， 最终经进一步纯化获得氯化钾晶体。 该方法首先进行预处理将原料中的氯化钠除去， 成为 含较低钠浓度的原料， 再进行氯化钾的生产， 研究对象并非直接针对高钠钾矿盐。 1. A method and a device for producing potassium chloride from carnallite (CN1260323). The invention uses a carnallite slurry as a raw material, and thickens and fractionates sodium chloride and reverse flotation to obtain coarse fine haw. The filter cake is then subjected to crystallization to obtain crude potassium base, which is finally purified to obtain potassium chloride crystals. The method firstly pretreats the sodium chloride in the raw material to become a raw material containing a lower sodium concentration, and then produces potassium chloride, and the research object is not directed to the high sodium potassium mineral salt.
2、 钾石盐与光卤石的混合矿中提取氯化钾的方法（CN1259486), 该发明将盐田采收 的钾石盐与光卤石混合矿经破碎后， 加入饱和卤水磨矿， 而后进行浮选， 经过滤、 干燥得 到氯化钾固体， 关键在于在浮选的过程中使用了十八胺为捕捉剂、 羧甲基纤维素为抑制剂 用于提高氯化钾的回收率， 一方面原料不是以高钠钾矿盐， 同时对于如何提高氯化钾产品
粒径未做探讨。 2. A method for extracting potassium chloride from a mixed mineral of potassium salt and carnallite (CN1259486), which is obtained by crushing a mixed salt of potassium salt and carnallite recovered in a salt field, and then adding a saturated brine to grind, and then Flotation, filtration and drying to obtain potassium chloride solid, the key is to use octadecylamine as a scavenger in the flotation process, and carboxymethyl cellulose as an inhibitor to increase the recovery rate of potassium chloride. The raw materials are not high sodium potassium minerals, but also how to improve potassium chloride products. The particle size has not been explored.
3、 细晶消除与膜耦合相结合的反浮选-冷结晶氯化钾生产方法 （CN101066769 ), 该 发明将首先通过反浮选制备低钠光卤石， 再用淡水分解、 结晶、 离心过滤干燥制 KC1， 再 用微滤回收溶解二次结晶获得较大颗粒 KC1。 研究对象为低钠光卤石而不是高钠光卤石。 3, fine crystal elimination combined with membrane coupling, reverse flotation - cold crystal potassium chloride production method (CN101066769), the invention will first prepare low sodium carnallite by reverse flotation, followed by fresh water decomposition, crystallization, centrifugal filtration The KC1 is dried, and the secondary crystal is dissolved by microfiltration to obtain a larger particle KC1. The study object was low sodium carnallite instead of high sodium carnallite.
通过对比， 本发明专利申请与上述三篇专利公开文献存在本质的不同。 By contrast, the patent application of the present invention is substantially different from the above three patent publications.
发明内容 Summary of the invention
本发明的目的是克服现有技术的不足之处，提供一种高钠钾盐矿的冷分解结晶及浮选 方法制备大颗粒氯化钾的系统及工艺， 即以高钠钾盐矿为原料， 采用冷分解结晶工艺控制 及浮选分离获得大颗粒氯化钾产品的方法， 同时根据工艺参数提出实现氯化钾产品粒度控 制的结晶器结构及操作参数。 The object of the present invention is to overcome the deficiencies of the prior art, and provide a system and a process for preparing large-particle potassium chloride by cold decomposition crystallization and flotation of high sodium potassium salt ore, that is, using high sodium potassium salt ore as raw material. A method for obtaining large-particle potassium chloride products by cold decomposition crystallization process control and flotation separation, and at the same time, according to the process parameters, a crystallizer structure and operating parameters for realizing the particle size control of the potassium chloride product are proposed.
本发明实现目的的技术方案是： The technical solution for achieving the object of the present invention is:
一种高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的系统， 由喂料控制系 统、 冷分解结晶器、 细晶消除罐及淡水储罐依次连接而成， 在冷分解结晶器内设置有搅拌 桨， 在细晶消除罐与冷分解结晶器之间还安装有输送循环液的循环泵， 在淡水储罐的供给 管路上安装有水泵。 Cold decomposition crystallization and flotation method of high-sodium potassium salt ore to prepare large-particle potassium chloride system, which is formed by feeding control system, cold decomposition crystallizer, fine crystal elimination tank and fresh water storage tank in sequence, in cold A stirring paddle is disposed in the decomposition crystallizer, and a circulation pump for conveying the circulating liquid is further installed between the fine crystal eliminating tank and the cold decomposition crystallizer, and a water pump is installed in the supply line of the fresh water storage tank.
而且， 所述冷分解结晶器包括内导流筒和外导流筒、 搅拌桨、 搅拌电机、 溢流槽、 顶 部进料口、 顶部溢流口、 底部排料口， 其底部为 ω型结构。 Moreover, the cold decomposition crystallizer comprises an inner guide tube and an outer guide tube, a stirring paddle, a stirring motor, an overflow tank, a top feed port, a top overflow port, a bottom discharge port, and an ω-type structure at the bottom thereof. .
而且，所述冷分解结晶器的搅拌桨为单层桨叶结构或双层桨叶结构， 搅拌桨叶为平直 叶式或推进式， 所述溢流槽内的溢流堰板为齿形结构。 Further, the agitating paddle of the cold decomposition crystallizer is a single-layer blade structure or a double-layer blade structure, the agitating blade is a flat blade type or a propulsion type, and the overflow weir plate in the overflow groove is a tooth-shaped structure.
一种高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的工艺， 步骤是： A process for preparing large-particle potassium chloride by cold decomposition crystallization and flotation of high-sodium potassium salt ore, the steps are:
(1)将氯化钠质量百分含量为 30%〜60%的高钠钾盐矿经筛孔直径为 lmm~10mm的标准 筛筛分， 筛下物作为进料并采用连续螺旋喂料系统连续加入冷分解结晶器， 高钠钾盐矿的 喂料速率为 lkg/h〜500t/h， 循环液中 MgCl2的质量百分比浓度为 15% -30%, 在冷分解结 晶器的停留时间为 lh~5h， 操作温度为 20°C~40°C， 平直叶式或推进式搅拌桨的搅拌速度 为 20rpm~700rpm， 冷分解结晶器内得到大颗粒氯化钾产品； (1) The high-sodium potassium salt mine with a sodium chloride mass percentage of 30%~60% is sieved through a standard sieve with a mesh diameter of lmm~10mm, and the sieved material is used as a feed and a continuous screw feeding system is adopted. Continuously adding cold decomposition crystallizer, the feed rate of high sodium potassium salt mine is lkg/h~500t/h, the mass concentration of MgCl 2 in the circulating liquid is 15% -30%, and the residence time in the cold decomposition crystallizer is Lh~5h, the operating temperature is 20 °C ~ 40 °C, the stirring speed of the straight leaf type or propeller type stirring paddle is 20 rpm~700 rpm, and the large particle potassium chloride product is obtained in the cold decomposition crystallizer;
(2)对步骤 (1)中冷分解结晶器顶部得到的氯化钾细晶产品以母液溢流的形式进入细晶 消除罐，将流量为 0.15IJh〜150m3/h的淡水连续加入细晶消除罐以溶解罐内的氯化钾细晶， 溶解氯化钾后细晶消除罐内的液体为循环液， 该循环液经循环泵输送连续返回冷分解结晶 器， 冷分解结晶器中循环液的加入速率为 1.3 kg/h ~2500t/h; (2) The potassium chloride fine crystal product obtained at the top of the cold decomposition crystallizer in the step (1) enters the fine crystal elimination tank in the form of mother liquor overflow, and the fresh water having a flow rate of 0.15 IJh to 150 m 3 /h is continuously added to the fine crystal. The can is eliminated to dissolve the fine crystal of potassium chloride in the tank, and after dissolving the potassium chloride, the fine crystal eliminates the liquid in the tank as a circulating liquid, and the circulating liquid is continuously returned to the cold decomposition crystallizer by the circulation pump, and the circulating liquid in the cold decomposition crystallizer The rate of addition is 1.3 kg / h ~ 2500 t / h ;
(3)对步骤 (2)中得到的氯化钾产品与氯化钠混合物从冷分解结晶器底部连续排出，底流
产品在与冷分解结晶器分解液组成相同的筛分液中经 10目~50目泰勒标准筛筛分，筛分液 为与冷分解结晶器内母液相同， 筛下物经抽滤后的滤饼在浮选器内进行调浆后并经一次粗 选、 两次精选后的滤饼在无水乙醇中筛分得到氯化钾产品。 (3) continuously discharging the potassium chloride product obtained in the step (2) and the sodium chloride mixture from the bottom of the cold decomposition crystallizer, the underflow The product is sieved through a 10 mesh to 50 mesh Taylor standard sieve in the same sieve composition as the decomposition liquid of the cold decomposition crystallizer. The sieve liquid is the same as the mother liquid in the cold decomposition crystallizer, and the sieved material is filtered by suction filtration. The cake is slurried in a flotation machine and sieved in absolute ethanol through a rough selection and twice selected filter cake to obtain a potassium chloride product.
而且， 所述步骤 (3)中筛分液为与冷分解结晶器内母液相同的卤水或无水乙醇。 Further, the sieving liquid in the step (3) is the same brine or absolute ethanol as the mother liquid in the cold decomposition crystallizer.
本发明的优点和有益效果为： The advantages and benefits of the present invention are:
1、 本发明针对高钠钾盐矿为原料生产氯化钾过程， 采用冷分解结晶控制氯化钾产品 粒度-浮选方法分离结晶底流产品的工艺， 可获得大颗粒氯化钾晶体产品， 对于进一步优化 选矿厂工程设计的设备选型， 提高设备运行的可靠性和稳定性， 降低设备运行费用具有重 要意义， 同时节省生产过程中离心分离操作和干燥过程的运行成本， 降低产品的综合成本， 克服了现有以高钠钾盐矿直接分解获得氯化钾产品小、 离心分离过程和干燥过程的运行成 本高且多采用后序造粒技术形成最终产品的不足之处。 1. The present invention is directed to a process for producing potassium chloride by using a high-sodium potassium salt ore as a raw material, and a process for separating a crystalline underflow product by a particle size-flotation method of a potassium chloride product by cold decomposition crystallization, thereby obtaining a large-particle potassium chloride crystal product, It is of great significance to further optimize the equipment selection of the engineering design of the concentrator, improve the reliability and stability of the operation of the equipment, and reduce the operating cost of the equipment. At the same time, it saves the operating cost of the centrifugal separation operation and the drying process in the production process, and reduces the overall cost of the product. The invention overcomes the shortcomings of the direct decomposition of high-sodium potassium salt ore to obtain a small potassium chloride product, high operating cost of the centrifugal separation process and the drying process, and the use of the subsequent granulation technology to form the final product.
2、本发明通过设定工艺及参数控制条件，针对氯化钠（NaCl)质量百分含量为 30%〜 60%的高钠钾盐矿生产氯化钾， 实现以高钠钾盐矿为原料生产氯化钾过程中对氯化钾晶体 产品粒度的控制， 获得的产品氯化钾平均粒度为 0.15mm〜0.35mm， 提高了以高钠钾盐矿 为原料生产氯化钾产品的市场竞争力， 经济效益十分显著， 市场前景广阔。 2. The invention produces potassium chloride by setting the process and parameter control conditions for the high sodium salt mine of sodium chloride (NaCl) content of 30%~60%, realizing the use of high sodium potassium salt ore as raw material. In the process of producing potassium chloride, the particle size of the potassium chloride crystal product is controlled, and the obtained product has an average particle size of 0.15 mm to 0.35 mm, which improves the market competitiveness of producing potassium chloride products by using high sodium potassium salt ore as raw material. The economic benefits are very significant and the market prospect is broad.
附图说明 DRAWINGS
图 1为本发明的工艺流程图； Figure 1 is a process flow diagram of the present invention;
图 2为本发明的系统结构示意图； 2 is a schematic structural view of a system of the present invention;
图 3为本发明的冷分解结晶器结构主视图； Figure 3 is a front elevational view showing the structure of the cold decomposition crystallizer of the present invention;
图 4为图 3的 A-A向结构示意图。 Fig. 4 is a schematic view showing the structure of the A-A direction of Fig. 3.
具体实肺式 Specific lung
下面通过具体实施例对本发明作进一步详述， 以下实施例只是描述性的， 不是限定性 的， 不能以此限定本发明的保护范围。 The invention is further described in detail below by way of specific examples. The following examples are merely illustrative and not limiting, and the scope of the invention is not limited thereto.
一种高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的系统，参见图 2、 3、 4， 整个系统由喂料控制系统 1、 冷分解结晶器 3、 细晶消除罐 6及淡水储罐 8依次连接而成， 冷分解结晶器连接有恒温水浴器 2， 冷分解结晶器可设有夹套以保持结晶器内料液在设定 的操作温度， 夹套内的介质可为水， 可采用恒温水浴器或蒸汽加热及控制进入结晶器夹套 内水的温度， 在冷分解结晶器内设置有搅拌桨 4。 在细晶消除罐与冷分解结晶器之间还安 装有循环液的循环泵 5， 在淡水储罐的供给管路上安装有水泵 7。 A system for preparing large-particle potassium chloride by cold decomposition crystallization and flotation of high-sodium potassium salt ore, see Figures 2, 3, and 4, the whole system is eliminated by feed control system 1, cold decomposition crystallizer 3, fine crystal The tank 6 and the fresh water storage tank 8 are connected in sequence, and the cold decomposition crystallizer is connected with the constant temperature water bath 2, and the cold decomposition crystallizer can be provided with a jacket to keep the liquid in the crystallizer at the set operating temperature, in the jacket. The medium may be water, and the temperature of the water entering the crystallizer jacket may be heated and controlled by a constant temperature water bath or steam, and a stirring paddle 4 is disposed in the cold decomposition crystallizer. A circulation pump 5 is also installed between the fine crystal elimination tank and the cold decomposition crystallizer, and a water pump 7 is installed in the supply line of the fresh water storage tank.
冷分解结晶器的具体结构参见图 3、 4， 包括内导流筒和外导流筒、 搅拌桨、 搅拌电
机、 溢流槽、 顶部溢流口、 底部排料口， 其底部为 ω型结构。 所述搅拌桨为单层桨叶结构 或双层桨叶结构， 搅拌桨叶为平直叶式或推进式； 冷分解结晶器所用材料为铸铁、合金钢、 碳钢或不锈钢， 溢流槽内的溢流堰板为齿形结构。 Refer to Figures 3 and 4 for the specific structure of the cold decomposition crystallizer, including the inner guide tube and the outer guide tube, the stirring paddle, and the stirring electric The machine, the overflow tank, the top overflow port, and the bottom discharge port have an ω-shaped structure at the bottom. The agitating paddle is a single-layer blade structure or a double-layer blade structure, and the agitating paddle is a flat blade type or a propulsion type; the material used for the cold decomposition crystallizer is cast iron, alloy steel, carbon steel or stainless steel, overflow in the overflow tank The flow board is a toothed structure.
下面以三个实施例来具体叙述本发明申请的制备工艺： The preparation process of the present application is specifically described below in three examples:
实施例 1: Example 1:
一种高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的工艺， 具体步骤如下： A process for preparing large-particle potassium chloride by cold decomposition crystallization and flotation of high-sodium potassium salt ore, the specific steps are as follows:
(1)将氯化钠质量百分含量为 29.84%的高钠钾盐矿经筛孔直径为 4mm的标准筛筛分， 筛下物作为进料并采用连续螺旋喂料系统连续加入冷分解结晶器， 高钠钾盐矿的喂料速率 为 2.38kg/h， 循环液中 MgCl2的质量百分比浓度为 23%， 结晶器的停留时间为 3.55小时， 操作温度为 25°C， 推进式搅拌桨的搅拌速度为 400rpm， 结晶器内得到大颗粒氯化钾产品。 (1) The high-sodium potassium salt mine with a sodium chloride mass percentage of 29.84% is sieved through a standard sieve having a mesh diameter of 4 mm, and the sieved material is fed as a feed and continuously added to the cold decomposition crystallization by a continuous screw feeding system. , the feed rate of high sodium potassium salt mine is 2.38kg / h, the mass concentration of MgCl 2 in the circulating fluid is 23%, the residence time of the crystallizer is 3.55 hours, the operating temperature is 25 ° C, the propulsion stirring paddle The stirring speed was 400 rpm, and a large particle potassium chloride product was obtained in the crystallizer.
(2)对步骤 (1)中结晶器顶部得到的氯化钾细晶产品以母液溢流的形式进入细晶消除罐， 将流量为 0.65IJh的淡水连续加入细晶消除罐以溶解罐内的氯化钾细晶， 溶解氯化钾后细 晶消除罐内的液体为循环液， 该循环液经循环泵输送连续返回结晶器， 结晶器中循环液的 加入速率为 5.87kg/h。 (2) The potassium chloride fine crystal product obtained at the top of the crystallizer in the step (1) enters the fine crystal elimination tank in the form of mother liquor overflow, and the fresh water having a flow rate of 0.65 IJh is continuously added to the fine crystal elimination tank to dissolve the inside of the tank. The fine crystal of potassium chloride dissolves the potassium chloride and dissolves the liquid in the tank as a circulating liquid. The circulating liquid is continuously returned to the crystallizer by the circulating pump, and the circulation rate of the circulating liquid in the crystallizer is 5.87 kg/h.
(3)对步骤 (2)中得到的氯化钾产品与氯化钠混合物从结晶器底部连续排出，底流产品在 与结晶器分解液组成相同的筛分液中经 32目 （0.5mm)泰勒标准筛筛分， 筛分液为与冷分 解结晶器内母液相同的液体 （卤水） 或无水乙醇； 筛下物经抽滤后的滤饼在浮选器内进行 调浆后并经一次粗选、 两次精选后的滤饼在无水乙醇中筛分得到氯化钾产品。 (3) The potassium chloride product obtained in the step (2) and the sodium chloride mixture are continuously discharged from the bottom of the crystallizer, and the underflow product is subjected to 32 mesh (0.5 mm) Taylor in the same sieve liquid as the crystallizer decomposition liquid. Standard sieve, the sieve liquid is the same liquid (brine) or absolute ethanol as the mother liquid in the cold decomposition crystallizer; the filter cake after the filtration is filtered in the flotation machine and then coarsened. The selected and filtered cakes were sieved in absolute ethanol to obtain a potassium chloride product.
实验结果为： The experimental results are:
KC1的平均粒径为 0.18mm， KC1的收率为 58%。 The average particle diameter of KC1 was 0.18 mm, and the yield of KC1 was 58%.
实施例 2: Example 2:
一种高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的工艺， 具体步骤如下： A process for preparing large-particle potassium chloride by cold decomposition crystallization and flotation of high-sodium potassium salt ore, the specific steps are as follows:
(1)氯化钠质量百分含量为 42.50%的高钠钾盐矿经筛孔直径为 6mm的标准筛筛分，筛 下物作为进料并采用连续螺旋喂料系统连续加入冷分解结晶器， 高钠钾盐矿的喂料速率为 3.95kg/h, 循环液中 MgCl2的质量百分比浓度为 25%， 结晶器的停留时间为 2.26小时， 操 作温度为 27°C， 平直式搅拌桨的搅拌速度为 600rpm， 结晶器内得到大颗粒氯化钾产品。 (1) The high-sodium potassium salt mine with a sodium chloride mass percentage of 42.50% is sieved through a standard sieve having a mesh diameter of 6 mm, and the sieved material is fed as a feed and continuously added to the cold decomposition crystallizer by a continuous screw feeding system. , the feed rate of high sodium potassium salt mine is 3.95kg / h, the mass concentration of MgCl 2 in the circulating liquid is 25%, the residence time of the crystallizer is 2.26 hours, the operating temperature is 27 ° C, the straight stirring paddle The stirring speed was 600 rpm, and a large particle potassium chloride product was obtained in the crystallizer.
(2)对步骤 (1)中结晶器顶部得到的氯化钾细晶产品以母液溢流的形式进入细晶消除罐， 将流量为 0.23IJh的淡水连续加入细晶消除罐以溶解罐内的氯化钾细晶， 溶解氯化钾后细 晶消除罐内的液体为循环液， 该循环液经循环泵输送连续返回结晶器， 结晶器中循环液的 加入速率为 5.87kg/h。
(3)对步骤 (2)中得到的氯化钾产品与氯化钠混合物从结晶器底部连续排出，底流产品在 与结晶器分解液组成相同的筛分液中经 32目 （0.5mm)泰勒标准筛筛分， 筛分液为与冷分 解结晶器内母液相同的液体 （卤水） 或无水乙醇； 筛下物经抽滤后的滤饼在浮选器内进行 调浆后并经一次粗选、 两次精选后的滤饼在无水乙醇中筛分得到氯化钾产品。 (2) The potassium chloride fine crystal product obtained at the top of the crystallizer in the step (1) enters the fine crystal elimination tank in the form of mother liquor overflow, and the fresh water having a flow rate of 0.23 IJh is continuously added to the fine crystal elimination tank to dissolve the inside of the tank. The fine crystal of potassium chloride dissolves the potassium chloride and dissolves the liquid in the tank as a circulating liquid. The circulating liquid is continuously returned to the crystallizer by the circulating pump, and the circulation rate of the circulating liquid in the crystallizer is 5.87 kg/h. (3) The potassium chloride product obtained in the step (2) and the sodium chloride mixture are continuously discharged from the bottom of the crystallizer, and the underflow product is subjected to 32 mesh (0.5 mm) Taylor in the same sieve liquid as the crystallizer decomposition liquid. Standard sieve, the sieve liquid is the same liquid (brine) or absolute ethanol as the mother liquid in the cold decomposition crystallizer; the filter cake after the filtration is filtered in the flotation machine and then coarsened. The selected and filtered cakes were sieved in absolute ethanol to obtain a potassium chloride product.
实验结果为： The experimental results are:
KC1的平均粒径为 0.16mm， KC1的收率为 51%。 The average particle diameter of KC1 was 0.16 mm, and the yield of KC1 was 51%.
实施例 3: Example 3:
一种高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的工艺， 具体步骤如下： A process for preparing large-particle potassium chloride by cold decomposition crystallization and flotation of high-sodium potassium salt ore, the specific steps are as follows:
(1)将氯化钠质量百分含量为 39.06%的高钠钾盐矿经筛孔直径为 8mm的标准筛筛分， 筛下物作为进料并采用连续螺旋喂料系统连续加入冷分解结晶器， 高钠钾盐矿的喂料速率 为 2.66kg/h， 循环液中 MgCl2的质量百分比浓度为 24%， 结晶器的停留时间为 3.50小时， 操作温度为 35°C， 推进式搅拌桨的搅拌速度为 400rpm， 结晶器内得到大颗粒氯化钾产品。 (1) The high-sodium potassium salt mine with a sodium chloride mass percentage of 39.06% is sieved through a standard sieve having a mesh diameter of 8 mm, and the sieved material is fed as a feed and continuously added to the cold decomposition crystallization by a continuous screw feeding system. , the feed rate of high sodium potassium salt mine is 2.66kg / h, the mass concentration of MgCl 2 in the circulating liquid is 24%, the residence time of the crystallizer is 3.50 hours, the operating temperature is 35 ° C, the propulsion stirring paddle The stirring speed was 400 rpm, and a large particle potassium chloride product was obtained in the crystallizer.
(2)对步骤 (1)中结晶器顶部得到的氯化钾细晶产品以母液溢流的形式进入细晶消除罐， 将流量为 0.49IJh的淡水连续加入细晶消除罐以溶解罐内的氯化钾细晶， 溶解氯化钾后细 晶消除罐内的液体为循环液， 该循环液经循环泵输送连续返回结晶器， 结晶器中循环液的 加入速率为 5.03kg/h。 (2) The potassium chloride fine crystal product obtained at the top of the crystallizer in the step (1) enters the fine crystal elimination tank in the form of mother liquor overflow, and the fresh water having a flow rate of 0.49IJh is continuously added to the fine crystal elimination tank to dissolve the inside of the tank. The fine crystal of potassium chloride dissolves the potassium chloride and dissolves the liquid in the tank as a circulating liquid. The circulating liquid is continuously returned to the crystallizer by the circulating pump, and the circulation rate of the circulating liquid in the crystallizer is 5.03 kg/h.
(3)对步骤 (2)中得到的氯化钾产品与氯化钠混合物从结晶器底部连续排出，底流产品在 与结晶器分解液组成相同的筛分液中经 32目 （0.5mm)泰勒标准筛筛分， 筛分液为与冷分 解结晶器内母液相同的液体 （卤水） 或无水乙醇； 筛下物经抽滤后的滤饼在浮选器内进行 调浆后并经一次粗选、 两次精选后的滤饼在无水乙醇中筛分得到氯化钾产品。 (3) The potassium chloride product obtained in the step (2) and the sodium chloride mixture are continuously discharged from the bottom of the crystallizer, and the underflow product is subjected to 32 mesh (0.5 mm) Taylor in the same sieve liquid as the crystallizer decomposition liquid. Standard sieve, the sieve liquid is the same liquid (brine) or absolute ethanol as the mother liquid in the cold decomposition crystallizer; the filter cake after the filtration is filtered in the flotation machine and then coarsened. The selected and filtered cakes were sieved in absolute ethanol to obtain a potassium chloride product.
实验结果为： The experimental results are:
KC1的平均粒径为 0.20mm， KC1的收率为 56%。
The average particle diameter of KC1 was 0.20 mm, and the yield of KC1 was 56%.
Claims
1、一种高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的系统， 其特征在于: 由喂料控制系统、 冷分解结晶器、 细晶消除罐及淡水储罐依次连接而成， 在冷分解结晶器 内设置有搅拌桨， 在细晶消除罐与冷分解结晶器之间还安装有输送循环液的循环泵， 在淡 水储罐的供给管路上安装有水泵。 1. A system for preparing large particles of potassium chloride by cold decomposition crystallization and flotation of high-sodium potassium salt ores, which is characterized by: consisting of a feeding control system, a cold decomposition crystallizer, a fine crystal elimination tank and a fresh water storage tank in sequence A stirring paddle is installed in the cold decomposition crystallizer, a circulation pump for transporting circulating liquid is installed between the fine crystal elimination tank and the cold decomposition crystallizer, and a water pump is installed on the supply pipeline of the fresh water storage tank.
2、 根据权利要求 1所述的高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的 系统， 其特征在于： 所述冷分解结晶器包括内导流筒和外导流筒、 搅拌桨、 搅拌电机、 溢 流槽、 顶部进料口、 顶部溢流口、 底部排料口， 其底部为 ω型结构。 2. A system for preparing large particle potassium chloride by cold decomposition crystallization and flotation of high-sodium potassium salt ore according to claim 1, characterized in that: the cold decomposition crystallizer includes an inner guide tube and an outer guide tube The drum, stirring paddle, stirring motor, overflow tank, top feed port, top overflow port, and bottom discharge port have a ω-shaped structure at the bottom.
3、 根据权利要求 1所述的高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的 系统， 其特征在于： 所述冷分解结晶器的搅拌桨为单层桨叶结构或双层桨叶结构， 搅拌桨 叶为平直叶式或推进式， 所述溢流槽内的溢流堰板为齿形结构。 3. A system for preparing large particles of potassium chloride by cold decomposition crystallization and flotation of high-sodium potassium salt ores according to claim 1, characterized in that: the stirring paddle of the cold decomposition crystallizer has a single-layer paddle structure Or a double-layer blade structure, the stirring blades are straight blade type or propelling type, and the overflow weir plate in the overflow tank is a tooth-shaped structure.
4、一种高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的工艺， 其特征在于: 步骤是： 4. A process for preparing large particles of potassium chloride by cold decomposition crystallization and flotation of high-sodium potassium salt ores, which is characterized by: The steps are:
(1)将氯化钠质量百分含量为 30%〜60%的高钠钾盐矿经筛孔直径为 lmm~10mm的标准 筛筛分， 筛下物作为进料并采用连续螺旋喂料系统连续加入冷分解结晶器， 高钠钾盐矿的 喂料速率为 lkg/h〜500t/h， 循环液中 MgCl2的质量百分比浓度为 15% -30% , 在冷分解结 晶器的停留时间为 lh~5h， 操作温度为 20°C ~40°C， 平直叶式或推进式搅拌桨的搅拌速度 为 20rpm~700rpm， 冷分解结晶器内得到大颗粒氯化钾产品； (1) Screen the high-sodium potassium salt ore with a sodium chloride mass percentage of 30% to 60% through a standard sieve with a mesh diameter of 1mm to 10mm, and use the undersize as feed and use a continuous spiral feeding system Continuously add the cold decomposition crystallizer, the feeding rate of the high sodium potassium salt ore is 1kg/h~500t/h, the mass percentage concentration of MgCl2 in the circulating liquid is 15% -30%, and the residence time in the cold decomposition crystallizer is lh~5h, the operating temperature is 20°C~40°C, the stirring speed of the straight blade or propeller stirring paddle is 20rpm~700rpm, and large particle potassium chloride products are obtained in the cold decomposition crystallizer;
(2)对步骤 (1)中冷分解结晶器顶部得到的氯化钾细晶产品以母液溢流的形式进入细晶 消除罐，将流量为 0.15IJh〜150m3/h的淡水连续加入细晶消除罐以溶解罐内的氯化钾细晶， 溶解氯化钾后细晶消除罐内的液体为循环液， 该循环液经循环泵输送连续返回冷分解结晶 器， 冷分解结晶器中循环液的加入速率为 1.3 kg/h ~2500t/h; (2) The potassium chloride fine crystal product obtained from the top of the cold decomposition crystallizer in step (1) enters the fine crystal elimination tank in the form of mother liquor overflow, and fresh water with a flow rate of 0.15IJh~ 150m3 /h is continuously added to the fine crystal The elimination tank is used to dissolve the fine crystals of potassium chloride in the tank. After the potassium chloride is dissolved, the liquid in the fine crystal elimination tank is the circulating liquid. The circulating liquid is transported by the circulating pump and continuously returned to the cold decomposition crystallizer. The circulating liquid in the cold decomposition crystallizer The addition rate is 1.3 kg/h ~2500t/h ;
(3)对步骤 (2)中得到的氯化钾产品与氯化钠混合物从冷分解结晶器底部连续排出，底流 产品在与冷分解结晶器分解液组成相同的筛分液中经 10目~50目泰勒标准筛筛分，筛分液 为与冷分解结晶器内母液相同， 筛下物经抽滤后的滤饼在浮选器内进行调浆后并经一次粗 选、 两次精选后的滤饼在无水乙醇中筛分得到氯化钾产品。 (3) The mixture of potassium chloride product and sodium chloride obtained in step (2) is continuously discharged from the bottom of the cold decomposition crystallizer, and the underflow product is passed through a 10-mesh screening liquid with the same composition as the decomposition liquid of the cold decomposition crystallizer. Sieve through a 50-mesh Taylor standard sieve. The sieved liquid is the same as the mother liquor in the cold decomposition crystallizer. The filter cake after suction filtration of the undersize material is slurried in the flotation device and undergoes one rough selection and two selections. The final filter cake is sieved in absolute ethanol to obtain potassium chloride product.
5、 根据权利要求 4所述的高钠钾盐矿的冷分解结晶及浮选方法制备大颗粒氯化钾的 工艺，其特征在于：所述步骤 (3)中筛分液为与冷分解结晶器内母液相同的卤水或无水乙醇。
5. A process for preparing large particle potassium chloride by cold decomposition crystallization and flotation method of high sodium potassium salt ore according to claim 4, characterized in that: in the step (3), the sieving liquid is mixed with cold decomposition crystallization The same brine or absolute ethanol as the mother liquid in the container.
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| CN107758696B (en) * | 2017-12-08 | 2019-09-17 | 中国科学院青海盐湖研究所 | A method of potassium chloride is prepared from the solid mineral of the magnesium of ammonium containing potassium |
| CN109574043A (en) * | 2019-02-11 | 2019-04-05 | 青海盐湖工业股份有限公司 | A kind of food grade sodium chloride and its production method |
| CN109794176B (en) * | 2019-03-25 | 2021-11-26 | 中蓝长化工程科技有限公司 | Fine crystal dissolving device of carnallite cold decomposition crystallizer |
| CN111170336B (en) * | 2020-02-24 | 2022-04-22 | 青海盐湖工业股份有限公司 | Method for preparing potassium chloride from carnallite raw ore |
| CN111470519B (en) * | 2020-05-06 | 2022-05-31 | 中国科学院青海盐湖研究所 | Method for preparing potassium chloride by using high-sodium carnallite |
| CN112723392A (en) * | 2020-12-02 | 2021-04-30 | 江苏昌吉利新能源科技有限公司 | Anhydrous lithium chloride continuous crystallization method |
| CN115159547A (en) * | 2022-08-12 | 2022-10-11 | 成都泰利创富锂业科技有限公司 | Method for improving recovery rate of potassium chloride prepared from raw ore carnallite |
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| CN2678736Y (en) * | 2004-03-04 | 2005-02-16 | 新疆罗布泊钾盐科技开发有限责任公司 | Top thrusting and down elevating mixed decomposing crystallizer |
| CN201458761U (en) * | 2009-08-18 | 2010-05-12 | 湖南丹化农资有限公司 | Vacuum cooling crystallizer for producing potassium nitrate |
| CN102963912A (en) * | 2012-12-25 | 2013-03-13 | 中蓝连海设计研究院 | Process for producing potassium chloride by using potassic salt ores |
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