CN101066769A - Reverse floatation-cold crystallization process for producing potassium chloride - Google Patents
Reverse floatation-cold crystallization process for producing potassium chloride Download PDFInfo
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Abstract
The reverse floatation and cold crystallization process for producing potassium chloride includes the following four steps: 1. reverse floatation to prepare low sodium carnallite; 2. decomposing low sodium carnallite in fresh water, crystallizing, centrifugally filtering and drying to prepare potassium chloride product; 3. microporous membrane filtering to recover fine potassium chloride crystal, dissolving, returning to potassium chloride crystallizer for secondary crystallization to prepare potassium chloride; and 4. returning the bittern for reuse. The process has potassium chloride yield up to 80 %, great potassium chloride crystal granularity and high product quality, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of production method of Repone K, particularly relate to the thin brilliant reverse flotation-cold crystallization Repone K production method that combines with the film coupling of eliminating, belong to field of inorganic chemical engineering.
Background technology
The development that the Repone K production technique has experienced decades is changed and constantly technical progress, produced the production method of many production Repone K therebetween, as: the salt pan recrystallization method, gravity separation method etc., all because of the reason of aspects such as environment, condition, weather, technology, some has also just carried out experiment or pilot scale and just does and stop, and does not realize suitability for industrialized production.These four kinds of production methods of cold decomposition direct flotation method, reverse flotation cold crystallization, thermosoling and adding halogen method have not only realized suitability for industrialized production in the Repone K in the Cha Er in China Qinghai sweat salt lake is produced, and have become the main method that potash fertilizer is produced.But thermosoling is because of its production cost height, and equipment corrosion is serious, and complicated operation etc. are former thereby stop.Cold decomposition direct flotation method, its production quality product is low, yields poorly, and yield is also low, can't realize large-scale production, but because of its technical maturity, simple to operate, be still most popular production technique.The adding halogen method production technique is than the above two, and production cost is low, good product quality, and granularity is also big, and the market competitiveness is strong, but this technology is raw material with flotation mill's decomposition nut liquid. industrial scale can not arbitrarily enlarge, and has limited the independence of this technology.
Cold crystallization technology is the new technology that development in recent years is got up, and is to produce the state-of-the-art production technique of Repone K with the salt pan carnallite at present, represents the direction of following sylvite ore purification technique development.The quality of crystalline product depends on crystal size and crystal mass, because each crystal grain is generated by nucleus, in certain magma volume, the nucleus turnout is few more, and it is more that crystal grain will be looked big, so the principle of cold crystallization is controlled the speed decomposition exactly and controlled fast crystallization.Its technological process is: in the crystallizer of particular design, by regulating factors such as density of magnesium chloride, rate of feeding, slurry temperature, the residence time, stirring intensity, particulate discharge rate and ratio in the decomposed solution, come the decomposition course of strict control carnallitite, make the potassium chloride particle of formation that good growth condition be arranged, thereby obtain the product of larger particles.But single cold crystallization technology is to the requirement height of carnallitite raw material, variation bad adaptability to the carnallite composition, in order to improve its adaptability, adopt and the joint flotation technology flow process, practice shows to be carried out cold crystallization earlier flotation effect is unsatisfactory again, reason is eutectic or the adhesive aggregation body that produces a large amount of Repone K and sodium-chlor in the cold crystallization process, has a strong impact on floatation process, causes concentrate grade low excessively.Therefore be improved to reverse flotation-cold crystallization technology after this technology.Reverse flotation cold crystallization technology, quality is good, the output height, continuity is strong, rate of recovery height, granularity is big, has the very strong market competitiveness, is the most advanced potash fertilizer production technique in the world today, extremely catches people's attention, and Cha Er sweat salt lake its method output has at present reached 1,300,000 tons.
Table 1.4 flotation process, thermosol crystallization process and three kinds of method relative merits of cold crystallization method are relatively
Table1.4?The?comparc?of?flotation，heat?dissolve?and?crystallization?and?cold?crystallization
| Technology category | Quality product | The product potassium rate of recovery | The unit product power consumption | Equipment corrosion | Facility investment | ||
| Granularity | Moisture | Impurity | |||||
| Cold decomposition-flotation process | Tiny 100～120 orders | ＞6% is difficult dry | Contain the medicament organic amine | 49～52％ | 1.0 | Gently | 1.0 |
| The thermosol crystallization process | Thick 50～30 orders | ＜3% is easily dry | Do not contain organic amine | 62～64％ | 1.8 | Seriously | 1.6 |
| Reverse flotation-cold crystallization method | Thick 50～40 orders | ＜3% is easily dry | 59～62 | 1.2 | Gently | 1.5 | |
Unit consumption of energy and construction investment are to be the relative value of standard setting with cold decomposition-flotation process in the notes table
1, cold decomposition one direct flotation method
This technology is research and application production technique the earliest, and all there is certain hydrophobicity on the surface of any material, if the hydrophobicity of two kinds of materials of a kind of material has very big-difference, and can be in view of the above with the two separation.Technological process is: shine with the beach, salt pan and produce carnallitite, decompose with fresh water again, utilize the difference of Repone K, sodium-chlor and magnesium chloride three solubleness to make carnallite decomposition post chlorization magnesium enter liquid phase, with flotation reagent Repone K being worked makes Repone K separate with sodium-chlor again.Accompanying drawing 2 is seen in its technical process.
Accompanying drawing 2 is cold decomposition-direct floatation process schema.
Main relative merits
Advantage: (1) technical process is simple, easy to operate; (2) this process exploitation is used early, and is quite ripe technically.
Shortcoming: (1) product granularity is thin, has only 0.088mm; (2) quality product is difficult for improving, and the system recoveries rate is lower.
2, reverse flotation one cold crystallization technology
Reverse flotation refers to be exactly the purpose product be not valuable mineral but useless mineral are just opposite with direct flotation so be called reverse flotation.This technology has been drawn the advantage of flotation and two kinds of technologies of cold crystallization.Adopt flotation technology can get low-sodium carnalite, satisfy of the requirement of cold crystallization technology to the carnallite raw material, overcome the shortcoming of cold crystallization technology to raw ore variation bad adaptability, adopt the cold crystallization technology can obtain then that particle is thick, purity is high, the measured product of matter, improved the physicals of product, overcome shortcomings such as floating product fine size, filtration and dry difficulty, thereby had development prospect.Chinese patent 97103513.X discloses a kind of reverse flotation-cold crystallization production technique (process for producing potassium chloride from carnallite).
The theoretical basis of carnallitite cold crystallization is the decomposition of control speed and controls fast crystallization, carnallitite exists the dissolving of Repone K and two reversible processes of crystallization of Repone K when decomposing, carnallitite formation saturated potassium chloride solution soluble in water before this, thus make Repone K in solution, separate out crystallization.And to obtain granularity Repone K crystal grain preferably.Must control first process is the dissolution rate of carnallitite.Dissolve too fast.Easily form too high Repone K degree of supersaturation, thereby produce a large amount of thin brilliant crystallization yields that influence.This method is to add the Na collecting agent in flotation.Its technical process such as accompanying drawing 3.
Accompanying drawing 3 is reverse flotation-cold crystallization technology.
Main relative merits
Advantage: (1) product granularity big (0.2mm), be easy to drying, appearance effect is good; (2) quality and the system recoveries rate of product have been improved.
Shortcoming: (1) technical process complexity, inconveniences such as operation control; (2) accuracy requirement is higher in flotation and crystalline operating process.
3, adding halogen method
Convert halogen and be exactly with Repone K, sodium-chlor and carnallitite altogether saturated mother liquor mix with magnesium chloride, sodium-chlor, the common saturated mother liquor of carnallitite, just have carnallitite and small amount of sodium chloride is separated out.Its mechanism is.Above-mentioned two kinds of mother liquor mixed solution system points have been fallen the carnallitite phase region.And be in water figure sodium-chlor and carnallitite solubility curve and carnallitite saturation plane downside.So mixture system is a hypersaturated state, it will separate out certain salt, because of it is in the carnallitite phase region, and at first separate out carnallitite, treat that carnallitite is saturated after, carnallitite and sodium-chlor are separated out jointly, to finish liquid be state of saturation up to converting halogen.This method is that F selects bittern and E and selects bittern and convert halogen and obtain low-sodium carnalite.
Its technical process such as Fig. 4.
Accompanying drawing 4 is the adding halogen method process flow sheet
Main relative merits:
Advantage: (1) product grade height.Can reach 98% and easy to control and adjust; (2) technology controlling and process is simple.Can realize automatic control; (3) liquid phase is many in this method process.Easily carry.And utilized discarded old halogen production cost low.
Shortcoming: (1) technology is raw material with flotation mill's decomposition nut liquid, and industrial scale can not arbitrarily enlarge; (2) technology is converted the difficult accurately grasp of halogen; (3) the system recoveries rate is low.The wasting of resources is more serious.
Summary of the invention
The objective of the invention is at the quality product of existing reverse flotation one cold crystallization technology existence relatively poor, the defective that the Repone K utilization ratio is lower is carried out significant improvement, carrying out using when reverse flotation separates sodium-chlor the high nanofiltration membrane of sodium chloride-containing composition that reclaims through nanofiltration to see through liquid, carrying out the cold decomposition magnesium chloride of carnallitite fine fodder, when Repone K is produced in crystallization, it is carefully brilliant to adopt microfiltration membrane to reclaim Repone K, the crystalline mother solution that microfiltration membrane sees through filters by nanofiltration membrane, the thin crystalline substance of dialyzate dissolving Repone K is prepared into saturated solution and is back in the crystallizer, the control potassium chloride concentration prevents the formation of supersaturated solution, thereby the quantity of the dissolution rate of Repone K and unit volume Repone K nucleus in the refined carnallite in the crystallization control device, when making the Repone K crystallization, oarse-grained crystal grain as much as possible, short grained crystal grain is as far as possible few.Improved the recovery utilization rate of Repone K.
The present invention realizes as follows:
(1) reverse flotation prepares low-sodium carnalite: it is to be raw material with the carnallitite, through sizing mixing, production processes such as reverse flotation, dense (), dehalogenation, obtain refined carnallite, be in the saturated solution of ratio of 15-40% promptly with raw material carnallitite adding carnallitite in solid-to-liquid ratio, the special-purpose flotation agent of fatty amide sodium-chlor that adds the 8-12 carbon of 100-400 gram by carnallitite per ton carries out reverse flotation two to three times, carry out sedimentation then and concentrate, filtering separation removes most of sodium-chlor and is prepared into sodium chloride-containing less than 6% refined carnallite.
(2) Repone K preparation: it is that the refined carnallite for preparing with step (1) is a raw material, get the Repone K finished product through decomposition and crystallization, dense (two), filtration drying, promptly the refined carnallite with step (1) preparation is a raw material, the fresh water decomposition, the crystallization that add the 750-1100 kilogram by refined carnallite per ton, carrying out sedimentation then concentrates, be prepared into wet Repone K through centrifugation then, wet Repone K drying is prepared into the Repone K finished product.
(3) the thin brilliant recycling of Repone K: it is thin brilliant in the microfiltration membrane recovery to produce the Repone K that produces in the Repone K process, behind fresh water dissolution, pumps into and carries out secondary crystal in the Repone K crystallizing pond, to make full use of the Repone K resource; Used micro-filtration membrane module is ceramic film component, metallic membrane assembly or organic tubular membrane component.Described microfiltration membrane aperture is the 0.1-10 micron.Operational condition is: temperature 15-50 ℃, entrance pressure 0.7-10bar goes out to press 0.6-9bar, pressure difference 0.1-1.5bar.Material can be: polyethersulfone (PES) polysulfone membrane (PS), polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF) (PVDF), stainless steel membrane, ceramic membrane.
(4) bittern reuse: the mother liquor behind the Crystallization Separation Repone K that microfiltration membrane is seen through is through the nanofiltration filtering separation, magnesium chloride concentrated solution and Repone K dialyzate, Repone K dialyzate cyclically utilizing is as the solvent of dissolving carnallitite.Solution returns reverse flotation and removes sodium-chlor when nanofiltration membrane dialyzate sodium-chlor composition is high, and the magnesium chloride concentrated solution is as the raw material of magnesium chloride comprehensive utilization.The used nanofiltration membrane component of bittern reuse is rolled membrane module, hollow fiber film assembly or tubular membrane component.Used nanofiltration membrane material is composite nanometer filtering film, polyether sulfone filtering film, polysulfone membrane (PES) nanofiltration membrane, polyamide (PA) nanofiltration membrane, cellulose acetate (CA) nanofiltration membrane, aromatic polyamides (APA) nanofiltration membrane, polyolefine nanofiltration membrane, SPSF (SPS) nanofiltration membrane, polyvinyl alcohol (PVA) nanofiltration membrane, the poly-piperazine amide composite membrane nanofiltration membrane of molecular weight cut off 100-500.When the used nanofiltration membrane component of bittern reuse was rolled membrane module, operational condition was: temperature 15-50 ℃, entrance pressure 5-40bar goes out to press 4.5-39.5bar, pressure difference 0.5-2.0bar.When the used nanofiltration membrane component of bittern reuse was tubular membrane component, operational condition was: temperature 15-50 ℃, entrance pressure 10-40bar goes out to press 9.5-39.5bar, pressure difference 0.5-2.0bar.When the used nanofiltration membrane component of bittern reuse was hollow fiber film assembly, operational condition was: temperature 15-50 ℃, entrance pressure 5-40bar goes out to press 4.5-39.5bar, pressure difference 0.5-2.0bar.
Present method and existing reverse flotation one cold crystallization technology relatively have following advantage:
(1) particle of product Repone K is big, the quality height
At the carnallitite fine fodder is raw material, when dissolving crystallized separation of produced Repone K, employing is prepared into saturated solution with the thin brilliant dissolving of Repone K and is back in the crystallizer, thereby prevent the formation of Repone K high density supersaturated solution, the dissolution rate of Repone K and the quantity of unit volume Repone K nucleus in the control refined carnallite, when making the Repone K crystallization, oarse-grained crystal grain as much as possible, short grained crystal grain is as far as possible few.Because the crystal grain of Repone K is big, water capacity is low, is easy to separate the quality product height of gained.
(2) Repone K and water utilization rate height
The rate of recovery of the product potassium of the production technique that adopts has only 59-62% now, in other words, has the potassium of 38-41% to be lost aborning, has not only caused the wasting of resources, and causes production cost to rise.The major cause that causes this waste is a Crystallization Separation Repone K and contain a large amount of Repone K in the mother liquor that produces, and these Repone K together discharge with bittern, have caused the significant wastage of water resources and potassium resource.The mother liquor that present method produces Crystallization Separation Repone K filters with nanofiltration, makes Repone K see through nanofiltration membrane and is present in the dialyzate, and magnesium chloride etc. see through nanofiltration membrane on a small quantity and are present in the concentrated solution.The dialyzate that will contain Repone K is back to the decomposition carnallitite, thereby has not only controlled the magnesium chloride decomposition rate of carnallitite and the crystallization velocity of Repone K, has improved the once through yield of potassium, makes it to reach more than 80%, has also improved the utilization ratio of water simultaneously.
Description of drawings
Fig. 1, the thin brilliant technological process of production block diagram of eliminating the reverse flotation-cold crystallization Repone K production method that combines with the film coupling
Specific embodiment
The present invention is further illustrated below in conjunction with accompanying drawing:
Embodiment 1
(carnallitite contains Repone K 21.7% to take by weighing 300 kilograms of carnallitite raw materials that pass through screening, magnesium chloride 27.7%, sodium-chlor 18%), size mixing in the saturated solution of 1 ton of carnallitite of adding, add 30 gram fatty amide floatating agent of sodium chloride reverse flotations then twice, carry out sedimentation then and concentrate (dense one), filtering separation removes most of sodium-chlor and is prepared into sodium chloride-containing 260 kilograms (refined carnallite contains Repone K 25.7% less than 6% refined carnallite (carnallitite fine fodder), magnesium chloride 32.2%, sodium-chlor 5.8%).With 260 kilograms of refined carnallites with 195 kilograms of fresh water decomposition and crystallization, carry out sedimentation then and concentrate (dense two), filtering separation gets 406 kilograms in 49 kilograms of Repone K work in-process and slurry, drying dewater 45.2 kilograms of Repone K finished products, yield is 69.4%, (with respect to the Repone K in the carnallitite) after testing, finished product contains Repone K 98.51%, water-insoluble 1.49%.
The thin crystalline substance of Repone K reclaims: with sedimentation concentrated (dense two), 406 kilograms of processes of the slurry of filtering separation gained micro-filtration filters, and gets 394 kilograms in 12 kilograms in thin crystalline substance of Repone K and mother liquor (bittern).The Repone K of gained thin brilliant 12 kilograms decompose with fresh water after, pump into and carry out secondary crystal in the Repone K crystallizing pond, to make full use of the Repone K resource, obtain coarse grained potassium chloride.The used micro-filtration membrane module of the thin brilliant recovery of Repone K is the ceramic film component in 0.5 micron in aperture, and operational condition is: temperature 15-50 ℃, entrance pressure 0.7-10bar goes out to press 0.6-9bar, pressure difference 0.1-1.5bar.
The recovery of Repone K in the bittern: 394 kilograms in the mother liquor that micro-filtration is filtered gained is through molecular weight cut off 100 tubular membrane component nanofiltration filtering separation and add the flushing of 239 kg of water, 183 kilograms of magnesium chloride solution concentrated solutions, 450 kilograms of dialyzates that contain Repone K.Repone K dialyzate cyclically utilizing is as the solvent of dissolving carnallitite, and the magnesium chloride concentrated solution is as the raw material of magnesium chloride comprehensive utilization.Tubular membrane component is a composite nanometer filtering film, and the operational condition of nanofiltration filtering separation is: temperature 15-50 ℃, entrance pressure 10-40bar goes out to press 9.5-38.5bar, pressure difference 0.5-2.0bar.
Embodiment 2
(carnallitite contains Repone K 21.7% to take by weighing 300 kilograms of carnallitite raw materials that pass through screening, magnesium chloride 27.7%, sodium-chlor 18%), the saturated solution of 1 ton of carnallitite of adding was sized mixing in (this saturated solution adds the carnallitite preparation with the Repone K dialyzate that reclaims), add 120 gram fatty amide floatating agent of sodium chloride reverse flotations then twice, carry out sedimentation then and concentrate (dense one), filtering separation removes most of sodium-chlor and is prepared into sodium chloride-containing 279 kilograms (refined carnallite contains Repone K 26.2% less than 6% refined carnallite (carnallitite fine fodder), magnesium chloride 32.2%, sodium-chlor 5.6%).With 279 kilograms of refined carnallites with 200 kilograms of fresh water decomposition and crystallization, carry out sedimentation then and concentrate (dense two), filtering separation gets 422 kilograms in 57 kilograms of Repone K work in-process and slurry, drying dewater 54.5 kilograms of Repone K finished products, yield is 83.7%, (with respect to the Repone K in the carnallitite) after testing, finished product contains Repone K 98.51%, water-insoluble 1.49%.
The thin crystalline substance of Repone K reclaims: with sedimentation concentrated (dense two), 422 kilograms of processes of the slurry of filtering separation gained micro-filtration filters, and gets 408 kilograms in 14 kilograms in thin crystalline substance of Repone K and mother liquor (bittern).The Repone K of gained thin brilliant 14 kilograms decompose with fresh water after, pump into and carry out secondary crystal in the Repone K crystallizing pond, to make full use of the Repone K resource, obtain coarse grained potassium chloride.The used micro-filtration membrane module of the thin brilliant recovery of Repone K is the metallic membrane assembly in 10 microns in aperture, and operational condition is: temperature 15-50 ℃, entrance pressure 0.7-10bar goes out to press 0.6-9bar, pressure difference 0.1-1.5bar.
The recovery of Repone K in the bittern: 408 kilograms in the mother liquor that micro-filtration is filtered gained is through molecular weight cut off 250 rolled membrane module nanofiltration filtering separation and add the flushing of 245 kg of water, 185 kilograms and 468 kilograms dialyzates that contain Repone K of magnesium chloride solution concentrated solution.Repone K dialyzate cyclically utilizing is as the solvent of dissolving carnallitite, and the magnesium chloride concentrated solution is as the raw material of magnesium chloride comprehensive utilization.The mould material of rolled membrane module is (polyamide (PA)) composite nanometer filtering film, and the operational condition of nanofiltration filtering separation is: temperature 15-50 ℃, entrance pressure 10-40bar goes out to press 9.5-38.5bar, pressure difference 0.5-2.0bar.
Embodiment 3
(carnallitite contains Repone K 21.7% to take by weighing 300 kilograms of carnallitite raw materials that pass through screening, magnesium chloride 27.7%, sodium-chlor 18%), the saturated solution of 750 kilograms of carnallitites of adding was sized mixing in (this saturated solution adds the carnallitite preparation with the Repone K dialyzate that reclaims), add 90 gram fatty amide floatating agent of sodium chloride reverse flotations then twice, carry out sedimentation then and concentrate (dense one), filtering separation removes most of sodium-chlor and is prepared into sodium chloride-containing 282 kilograms (refined carnallite contains Repone K 26.5% less than 6% refined carnallite (carnallitite fine fodder), magnesium chloride 32.1%, sodium-chlor 5.7%).With 282 kilograms of refined carnallites with 200 kilograms of fresh water decomposition and crystallization, carry out sedimentation then and concentrate (dense two), filtering separation gets 424 kilograms in 58 kilograms of Repone K work in-process and slurry, drying dewater 53.7 kilograms of Repone K finished products, yield is 82.5%, (with respect to the Repone K in the carnallitite) after testing, finished product contains Repone K 98.51%, water-insoluble 1.49%.
Repone K is thin brilliant to be reclaimed: sedimentation is concentrated (dense two), and 424 kilograms in the slurry of filtering separation gained filters through micro-filtration, 408.3 kilograms in Repone K thin brilliant 15.7 kilograms and mother liquor.The Repone K of gained thin brilliant 15.7 kilograms decompose with fresh water after, pump into and carry out secondary crystal in the Repone K crystallizing pond, to make full use of the Repone K resource, obtain coarse grained potassium chloride.The used micro-filtration membrane module of the thin brilliant recovery of Repone K is that the aperture is 5 microns polyethersulfone (PES) membrane module, and operational condition is: temperature 15-50 ℃, entrance pressure 0.7-10bar goes out to press 0.6-9bar, pressure difference 0.1-1.5bar.
Repone K in the bittern reclaims: 408.3 kilograms in the mother liquor that micro-filtration is filtered gained is through molecular weight cut off 500 rolled membrane module nanofiltration filtering separation and add the flushing of 250 kg of water, 200 kilograms and 458 kilograms dialyzates that contain Repone K of magnesium chloride solution concentrated solution.Repone K dialyzate cyclically utilizing is as the solvent of dissolving carnallitite, and the magnesium chloride concentrated solution is as the raw material of magnesium chloride comprehensive utilization.The mould material of rolled membrane module is SPSF (SPS) nanofiltration membrane, and the operational condition of nanofiltration filtering separation is: temperature 15-50 ℃, entrance pressure 10-30bar goes out to press 9.5-28.5bar, pressure difference 0.5-2.0bar.
Embodiment 4
The used micro-filtration membrane module of micro-filtration was that the aperture is 0.1 micron polyvinylidene difluoride (PVDF) (PVDF) membrane module when the thin crystalline substance of Repone K reclaimed, and operational condition is: temperature 15-45 ℃, entrance pressure 0.7-10bar goes out to press 0.6-9bar, pressure difference 0.1-1.5bar.It is cellulose acetate (CA) hollow fiber nanofiltration membrane of molecular weight cut off 500 that Repone K in the bittern reclaims used nanofiltration membrane component.Operational condition is: temperature 15-50 ℃, entrance pressure 5-35bar goes out to press 4.5-34.5bar, pressure difference 0.5-2.0bar.Other is identical with embodiment 1,2,3.
Embodiment 5
The used micro-filtration membrane module of micro-filtration was that the aperture is 3 microns a stainless steel membrane membrane module when the thin crystalline substance of Repone K reclaimed, and operational condition is: temperature 15-45 ℃, entrance pressure 0.7-10bar goes out to press 0.6-9bar, pressure difference 0.1-1.5bar.It is polysulfone membrane (PES) nanofiltration membrane of molecular weight cut off 350 that Repone K in the bittern reclaims used nanofiltration membrane component.Other is identical with embodiment 1,2,3,4.
Claims (10)
1, the thin brilliant reverse flotation-cold crystallization Repone K production method that combines with the film coupling of eliminating is characterized in that it comprises the steps:
(1) reverse flotation prepares low-sodium carnalite: it is raw material with the carnallitite, through sizing mixing, production processes such as reverse flotation, dense (), dehalogenation, obtain refined carnallite, be in the saturated solution of ratio of 15-40% promptly with raw material carnallitite adding carnallitite in solid-to-liquid ratio, the special-purpose flotation agent of fatty amide sodium-chlor that adds the 8-12 carbon of 100-400 gram by carnallitite per ton carries out reverse flotation two to three times, carry out sedimentation then and concentrate, filtering separation removes most of sodium-chlor and is prepared into sodium chloride-containing less than 6% refined carnallite.
(2) Repone K preparation: the refined carnallite with step (1) preparation is a raw material, get the Repone K finished product through decomposition and crystallization, dense (two), filtration drying, promptly the refined carnallite with step (1) preparation is a raw material, the fresh water decomposition, the crystallization that add the 750-1100 kilogram by refined carnallite per ton, carrying out sedimentation then concentrates, be prepared into wet Repone K through centrifugation then, wet Repone K drying is prepared into the Repone K finished product.
(3) the thin brilliant recycling of Repone K: it is thin brilliant in behind micro-filtrate membrane filtration recovery, the fresh water dissolution to produce the excess chlorination potassium that produces in the Repone K process, pumps into and carries out secondary crystal in the Repone K crystallizing pond, to make full use of the Repone K resource;
(4) bittern reuse: the Crystallization Separation Repone K mother liquor that microfiltration membrane is seen through is through the nanofiltration membrane filtering separation, get magnesium chloride trapped fluid and Repone K dialyzate, Repone K dialyzate cyclically utilizing is as the solvent of dissolving carnallitite, and the magnesium chloride concentrated solution is as the raw material of magnesium chloride comprehensive utilization.
2, the thin brilliant reverse flotation-cold crystallization Repone K production method that combines with the film coupling of eliminating according to claim 1, it is characterized in that: the recycling that the described Repone K of step (3) is thin brilliant be with contain the thin brilliant dense bittern (two) of Repone K by micro-filtrate membrane filtration separate thin crystalline substance of Repone K and bittern, the Repone K of gained is thin brilliant in after the fresh water decomposition, pump into and carry out secondary crystal in the Repone K crystallizing pond, to make full use of the Repone K resource, obtain coarse grained potassium chloride.
3, according to claim 1, the 2 described thin brilliant reverse flotation-cold crystallization Repone K production methods that combine with the film coupling of eliminating, it is characterized in that: it is ceramic film component, metallic membrane assembly or organic tubular membrane component that the thin crystalline substance of the described Repone K of step (3) reclaims used micro-filtration membrane module.
4, according to claim 1, the 2 described thin brilliant reverse flotation-cold crystallization Repone K production methods that combine with the film coupling of eliminating, it is characterized in that: the used microfiltration membrane scope of the described bittern reuse of step (3) is the 0.1-10 micron, operational condition is: temperature 15-50 ℃, entrance pressure 0.7-10bar, go out to press 0.6-9bar, pressure difference 0.1-1.5bar.Material can be: polyethersulfone (PES) polysulfone membrane (PS), polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF) (PVDF), stainless steel membrane, ceramic membrane.
5, the thin brilliant reverse flotation-cold crystallization Repone K production method that combines with the film coupling of eliminating according to claim 1, it is characterized in that: the described bittern reuse of step (4) is will be through mother liquor behind the thin brilliant separation Repone K of microfiltration membrane through the nanofiltration membrane filtering separation, trapped fluid is a magnesium chloride solution, dialyzate is a Klorvess Liquid, Repone K dialyzate cyclically utilizing is as the solvent of dissolving carnallitite, and the magnesium chloride concentrated solution is as the raw material of producing magnesium chloride.
6, according to claim 1, the 5 described thin brilliant reverse flotation-cold crystallization Repone K production methods that combine with the film coupling of eliminating, it is characterized in that: the used nanofiltration membrane component of the described bittern reuse of step (4) is rolled membrane module, hollow fiber film assembly or tubular membrane component.
7, according to claim 1, the 5 described thin brilliant reverse flotation-cold crystallization Repone K production methods that combine with the film coupling of eliminating, it is characterized in that: the used nanofiltration membrane material of the described bittern reuse of step (4) is composite nanometer filtering film, polyether sulfone filtering film, polysulfone membrane (PES) nanofiltration membrane, polyamide (PA) nanofiltration membrane, cellulose acetate (CA) nanofiltration membrane, aromatic polyamides (APA) nanofiltration membrane, polyolefine nanofiltration membrane, SPSF (SPS) nanofiltration membrane, polyvinyl alcohol (PVA) nanofiltration membrane, the poly-piperazine amide composite membrane nanofiltration membrane of molecular weight cut off 100-500.
8, according to claim 1, the 5 described thin brilliant reverse flotation-cold crystallization Repone K production methods that combine with the film coupling of eliminating, it is characterized in that: the used nanofiltration membrane component of the described bittern reuse of step (4) is that the operational condition of rolled membrane module is: temperature 15-50 ℃, entrance pressure 5-40bar, go out to press 4.5-39.5bar, pressure difference 0.5-2.0bar.
9, according to claim 1, the 5 described thin brilliant reverse flotation-cold crystallization Repone K production methods that combine with the film coupling of eliminating, it is characterized in that: the used nanofiltration membrane component of the described bittern reuse of step (4) is that the operational condition of tubular membrane component is: temperature 15-50 ℃, entrance pressure 5-40bar, go out to press 4.5-39.5bar, pressure difference 0.5-2.0bar.
10, according to claim 1, the 5 described thin brilliant reverse flotation-cold crystallization Repone K production methods that combine with the film coupling of eliminating, it is characterized in that: the used nanofiltration membrane component of the described bittern reuse of step (4) is that the operational condition of hollow fiber film assembly is: temperature 15-50 ℃, entrance pressure 5-35bar, go out to press 4.5-34.5bar, pressure difference 0.5-2.0bar.
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