CN1127219A - Preparing large crystal high purity potassium chloride by adding halogen method to remove Na and isolate K. - Google Patents
Preparing large crystal high purity potassium chloride by adding halogen method to remove Na and isolate K. Download PDFInfo
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- CN1127219A CN1127219A CN 95111124 CN95111124A CN1127219A CN 1127219 A CN1127219 A CN 1127219A CN 95111124 CN95111124 CN 95111124 CN 95111124 A CN95111124 A CN 95111124A CN 1127219 A CN1127219 A CN 1127219A
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Abstract
A kind of new method for separating potassium by blending bittern is that according to the calculated value of points concerned of KCl crystalline region of K+, Na+, Mg++//Cl--H2O hydrosaline system phase diagram, the adding amounts of various raw materials participating the reaction are determined, then in the crystallizer, the potassium is separated by blending bittern. The characteristic lies in that two kinds of KCl saturated bitterns with different concentrations are blended in the crystallizer, either carnallite bittern and KCl unsaturated solution and carnallite are added in or KCl saturated bittern and carnallite bittern and carnallite are added in. After blending bittern the crystals of KCl with pureness of 97% and 99.99% can be obtained once. The total yield of KCl is 77-87%, the crystal width is 0.45-1.0 mm, the length can come up to 5mm.
Description
The present invention relates to a kind of K with-15 °-+35 ℃
+, Na
+, Mg
++∥ Cl
--H
2O quaternary salt-water system isothermal phase diagram is produced the method for high purity potassium chloride for the basis.
Being the method that raw material is produced Repone K with the carnallitite both at home and abroad at present, all is based on potassium, sodium, magnesium ion. the quaternary salt-water system isothermal phase diagram that ∥ chlorion, water constitute.
Because the difference of potassium, sodium, Mg content in the carnallitite, position on potassium, sodium, magnesium ∥ chlorine, water figure is also inevitable different, simultaneously because the solubleness of magnesium chloride in water is more much bigger than Repone K, sodium-chlor, so at an easy rate magnesium chloride is at first separated from carnallitite, remaining is the mixture of solid-phase chlorination potassium and sodium-chlor, then the essence of producing the working method of Repone K with carnallitite is the separation method of Repone K and sodium-chlor, therefore, the ratio P of Repone K in the carnallitite and sodium-chlor
kBe as the significant parameter of weighing the carnallitite quality.
P
KBe worth different carnallitites, the position on potassium, sodium, magnesium ∥ chlorine water salt system phasor also can be different, and the method for its system potassium is also inevitable different.In phasor (accompanying drawing 1)
The P that G-1 is ordered
K≤ 0.8, the P that G-2 is ordered
K≤ 1.0,
The P that G-3 is ordered
K≤ 1.8, the P that G-4 is ordered
K〉=3.0.
The large-scale salt Tanaka who examines your sweat salt lake in China Qinghai critically promptly be will belong to potassium, sodium, magnesium ∥ chlorine, water quaternary salt-water system bittern through spontaneous evaporation, the carnallitite that makes, its P
K=1-2, general P
K=1.2.The external mechanical process that normally adopts is removed sodium-chlor in the carnallitite, makes P
k〉=3, then available cold crystallization method is processed this kind carnallitite, to produce pure Repone K.And the sodium-chlor in the carnallitite that is produced in your sweat salt lake is examined in the Qinghai of China critically, because of its granular size differs, then can't remove sodium with mechanical process, so occur after deliberation adopting the way of converting halogen to produce the high-quality carnallitite, its P salt Tanaka
K〉=3.
The novel method that this usefulness is converted the way system carnallitite of halogen is at present with converting unique purposes of halogen way salt manufacturing.
Work as P
K〉=3 o'clock, can adopt washing legal system potassium, promptly in carnallitite, add an amount of water, make magnesium chloride and sodium-chlor in the carnallitite all be dissolved in water, and Repone K is separated out, and can make the product that contains Repone K 90-93% after solid-liquid separation.
After also having water that carnallitite is all dissolved, revaporization falls unnecessary water, make sodium-chlor just in time saturated, and Repone K can be separated out, and again through solid-liquid separation, can make the product that KCE content is 90-95%, and this method is called " recrystallization method ".
On the basis of washing method, develop and a kind of new method, i.e. " cold crystallization method ", this method is lacked than the washing method amount of water, constantly drop in the crystallizer carnallitite and water according to a certain percentage, make material separate out Repone K under in crystallizer, circulating, after solid-liquid separation, washing drying, can make content and reach 95-98% Repone K product.This method is better than washing method, is that present technology is the simplest, quality and yield is the highest, benefit is best a kind of method.
Work as P
K≤ 1 o'clock, do not take off sodium earlier, just can't from this carnallitite, directly produce Repone K with above-mentioned each method, occurred utilizing stearylamine Repone K to be got " flotation process " of system Repone K as flotation agent thus from the system of carnallitite and water.Flotation process is compared production method with aforesaid method very simple, cost is close, but its Repone K product all is the fine powder body between 200 sieve meshes, product entrainment mother liquor amount is big when solid-liquid separation, also contain 5-6% moisture in the dried product, product is after stacking and long-distance transport, and the phenomenon of seriously forming lump is serious, and the user extremely has a headache to this.But before still not having the better method appearance at present, can only keep reluctantly and produce.
More than any method, all require the temperature of processing bittern can not be lower than 0 ℃, can't carry out otherwise produce.
The objective of the invention is to provide a kind of under the natural condition of not pressurizeing, not heating, when halogen temperature during at-5 °-35 ℃, the P of its carnallitite
K〉=3 or P
KCan utilize K under the condition of≤3 values
+, Na
+, Mg
++∥ Cl
--H
2O quaternary salt-water system isothermal phase diagram, the method that halogen is converted in employing is converted halogen with KCl crystallisation stage bittern WK-1 and carnallitite crystallisation stage bittern WGS and is analysed potassium in crystallizer, make highly purified macrocrystal Repone K product Q1 at last, basic potassium yield is 58-61% and Q2, and its potassium yield is 19-29%; The total recovery of the Repone K of product is 77-87%.Another object of the present invention is to have increased in this Repone K work flow to reclaiming the Repone K in the circulation fluid, the method that employing is converted halogen with the full altogether bittern WKN of potassium sodium and carnallitite stage bittern WGS is sloughed the sodium-chlor in the bittern, directly make low-sodium carnalite point bittern WG, this bittern is to be used to produce convert the essential intermediate raw material that halogen is analysed potassium or converted the stew in soy sauce low-sodium carnalite.
The present invention implements like this:
Set in the KCL crystallizing field in potassium, sodium, magnesium ∥ chlorine, the water quaternary salt-water system phasor
The G-0 point is for exploiting the raw ore carnallitite component point of gained, P naturally
K=1.17;
G-1 is a high-quality low-sodium carnalite component point after treatment, P
k=1.73;
The low-sodium carnalite that G-2 makes for the Repone K that reclaims in the system potassium flow process again, P
k=3.83;
WS-1 is bischofite point bittern point (36.5 ° of Be ');
WS-2 is bischofite stage bittern (36.5 ° of-37.5 ° of Be ');
WG is a carnallitite point bittern, also claims carnallite decomposition liquid (30.5 ° of-31.5 ° of Be ');
WGS carnallitite crystallisation stage bittern (30.5 ° of-36.5 ° of Be ');
WKN is the full altogether bittern (20 ° of-31 ° of Be ') of potassium sodium;
WP Repone K crystallisation stage saturated bittern (19.9 ° of-30.5 ° of Be ');
WKA Repone K saturated bittern (24 ° of-30.5 ° of Be ');
WK-1 Repone K saturated bittern (20 ° of-30.5 ° of Be ').
A converts halogen and analyses potassium district feed component point;
G converts the low-sodium carnalite that makes after the halogen, P
k〉=5.66;
L converts the material component point that halogen is analysed the carnallitite district.
Its typical work flow is to adopt Repone K crystallisation stage bittern WK-1, the WKA of two kinds of different concns or three kinds of bittern WK-1, WKA and carnallitite to select bittern WG to convert halogen in crystallizer, after circulating certain hour, can separate out the macrocrystal Repone K (containing KCl 99.99%) that requires granularity.Recovery to potassium the KCl crystallisation stage saturated bittern WP that has small-particle Repone K that discharges from the crystallizer overflow port has two kinds of methods:
1, in the little area of rainy steam output, WP and low-sodium carnalite G-2 dropped in second crystallizer analyse potassium, can make another part macrocrystal Repone K product (containing KCl 97%);
2, in the big area of arid steam output short of rain, WP flows directly in the spontaneous evaporation pond and analyses potassium, makes another part macrocrystal Repone K product (KCl 97%).
If require 97% Repone K product is all made 99.99% Repone K product, only need that 97% Repone K is made saturated potassium chloride solution WK-1, WKA and in crystallizer, analyse potassium by typically converting the halogen method, get final product the macrocrystal Repone K product of 99.99% content.
Full altogether bittern WKN of the potassium sodium of gained and carnallitite crystallisation stage bittern WGS convert halogen and go sodium to separate out new low-sodium carnalite G-2 in another container from decompose the carnallitite process, then reclaimed the transition Repone K in the work flow, constituted thus and converted halogen and take off the new method for processing that sodium is produced low-sodium carnalite G-2.
The carnallitite component point G-0 that is marked on the KCL crystallizing field on the phasor (accompanying drawing 2) begins, requirement is moved to the G-1 point, the method that moves is: carnallitite that G-0 order and bischofite point bittern are (in the input crystallizer of WG → WS-1), material circulates in crystallizer, more fine-grained carnallitite, sodium-chlor, water-insoluble can be suspended in the mother liquor, discharge from the overflow port on crystallizer top with mother liquor, particle carnallitite than volume particle size, sodium-chlor can sink to the bottom of crystallizer, emit from drain hole, promptly making component after solid-liquid separation is the high-quality carnallitite of G-1.
High-quality carnallitite G-1 and G-2 are added quantitative water decompose, refilter decomposed solution WG; Solid phase is that Repone K and sodium-chlor add quantitative water and makes the sodium-chlor CL, filter the full altogether bittern WKN of potassium sodium, filter solid-phase chlorination potassium to add water molten entirely, its component is the WK-1 point.The full altogether bittern WKN of each part potassium sodium of gained in the course of processing can be converted halogen with quantitative carnallitite stage bittern WGS analyse sodium, this analyses the sodium slip can flow into a settling bowl, gets sedimentation clear liquid WG, the sodium-chlor at the bottom of the eliminating pond.WKN and WGS convert halogen point point of the Q in the sodium-chlor district on phasor, and its liquidus point is the WG point.
The carnallitite of gained in the course of processing is selected bittern WG and bischofite stage bittern WS-2 to be converted halogen in 1: 2.5 ratio and separates out new carnallitite G-2, the P of this carnallitite
K〉=3.Total material component point of WG and WS-2 is the L point in the carnallitite crystallizing field on the phasor.
Saturated potassium chloride solution WK-1 with gained, in 1: the ratio of 3.5-4 adds carnallitite point bittern WG, in first crystallizer, convert halogen and analyse potassium, material circulated in crystallizer about 56 hours, can make the particle of the wide 0.45-1.0MM of potassium chloride, macrocrystal Repone K is discharged from the drain hole of the conical lower portion of crystallizer, after filtration, after the washing, drying, promptly get purity and be 99.99% macrocrystal Repone K, its potassium yield is 58-61%.Washings returns in the crystallizer and analyses potassium usefulness, the A point of the component of material point in the Repone K crystallizing field when converting halogen for converting halogen.
From the crystallizer overflow port with separate the saturated Repone K bittern WKA, the WP that obtain from crystallizer bottom drain hole and can directly enter spontaneous evaporation and analyse evaporative crystallization the potassium pond, can get purity through separation, washing, drying is 97.28%, the crystal width is the Repone K product of 0.15-0.5MM, and the yield of its potassium is 19-29%.And spontaneous evaporation is analysed the sodium-chlor of the bittern in the potassium pond when reaching capacity, and this bittern can pump into to be converted halogen and take off and take off sodium preparation, regeneration carnallitite G-2 in the sodium pond.
Another kind of working method to the Repone K saturated bittern of WKA and WP is to send in second crystallizer, add low-sodium carnalite G or G-2, circulated then 56 hours, from the drain hole of crystallizer bottom, discharge slip again, through separation, washing, drying, can make that to contain Repone K be 97-99.99%, the total recovery of its potassium is at 77-87%, the crystal grain width is 0.1 5-0.5MM, and length is the macrocrystal Repone K product of 2-5MM.
It is above-mentioned that to convert the complete processing that halogen takes off sodium regeneration carnallitite G-2 be to convert halogen to analyse the isolating novel method of indispensable potassium sodium in the potassium technology.
The advantage of this work flow is:
1, can adopt the raw material of natural light halogen masonry for the processing high purity potassium chloride;
2, analyse in the potassium flow process to adopt and convert halogen and take off the sodium method converting halogen, solved potassium sodium separation problem;
3, crystallizer can adopt universal crystallizer;
4, can in analysing the potassium crystallizer, directly make macrocrystal high purity potassium chloride product;
5, process operation can carry out in the scope of halogen temperature-15 °-+35 ℃, has got rid of in the past
Requirement remains on the restriction that can produce more than 0 ℃ in the halogen temperature.
The slip of emitting from the crystallizer bottom can get the Repone K product after solid-liquid separation, washing, drying, the analytical data of this Repone K product is listed in table 1-Q
1The analytical data of the Repone K product of separating out from the spontaneous evaporation pond is listed in table 1-Q
2Secondary crystal is 86.47% to the KCl total recovery in the throwing material.
Table 1 product K CL KCl% NaCl% MgCl
2% impurity % particle diameter (mm) yield % Q
199.99 0.02 0.001 0.001 0.45-1.2,61.67 Q
297.94 0.08 0.097 0.01 0.15-0.5 24.80
Through adopt the present invention fixed working method, can disposablely obtain purity and reach other Repone K of chemical pure level of 99.99%; The particle of this Repone K product is not the amorphous white powder of seeing usually, but a kind of transparent xln, the shape of the xln of product K Cl can artificially be controlled in certain scope with size, promptly converting the initially quantitative needle-like of input in crystallizer of halogen, slab-like Repone K crystal seed, its crystalline width is 0.4-0.9MM, after circulating 0.5-1 hour, get final product blowing, and liquid-solid separation, make the crystalline product of KCl of needle-like or slab-like, the crystalline trans D is generally at 0.45-1.2mm, and maximum can reach 1.2-1.5mm, and length can reach 5mm.Thereby solved the long-term indeterminable Repone K problem of caking easily.
As not adding crystal seed, in the time of making the crystal width of product reach 0.4 5-1.0MM, the time of circulating in crystallizer is about 56 hours.
Through above elaboration, can list a kind of typical principle flow process chart; And with embodiment the course of processing of the present invention is done detailed elaboration in conjunction with the accompanying drawings.
Accompanying drawing 2 is to convert halogen to take off sodium and analyse the position view of potassium technology general data on 20 ℃ of potassium, sodium, magnesium ∥ chlorine, water quaternary salt-water system isothermal phase diagram;
Accompanying drawing 3 is converted the stew in soy sauce high purity potassium chloride and is analysed the potassium mother liquor makes pure Repone K in the spontaneous evaporation crystallizing pond work flow material balance synoptic diagram for adopting KCl crystallisation stage saturated bittern and carnallitite crystallisation stage saturated bittern in crystallizer;
Accompanying drawing 4 is converted the work flow synoptic diagram that halogen takes off sodium for adopting full altogether bittern WKN of the potassium sodium of making gained in the potassium process and carnallitite stage bittern WGS;
Accompanying drawing 5 is that mother liquor WP after converting halogen analyse potassium in first crystallizer and low-sodium carnalite G or G-2 join the process flow diagram of analysing potassium in second crystallizer;
Accompanying drawing 6 is that the potassium mother liquor of analysing that adds in first crystallizer after kind is converted halogen and analysed potassium adds to the process flow diagram of analysing potassium in second crystallizer with low-sodium carnalite.
Below in conjunction with accompanying drawing and embodiment processing process of the present invention is described in detail: with reference under the normal pressure, 20 ℃ K+、Na
+、Mg
++∥Cl
-—H
2O quaternary water salt The system phase diagram mark takes off the various technology related components points that sodium is analysed potassium, and calculates various participation The raw material of reaction answer addition.
With reference to accompanying drawing 3, a kind of typical process operation of adopting adding halogen method to take off sodium, analysing potassium can be undertaken by following flow process:
Take 10 kilograms of salt pan carnallite G-0, add 50.87 kg of water chloromagnesite point bittern WS-1 gets 9.83 kilograms of low-sodium carnalite G-1 meters after stirring separation, contain sodium washing lotion 51.04 Kilogram discards. Take low-sodium carnalite G-2 the bittern-mixing pool processed again from carnallite, count 3.66 public affairs Jin adds 9.83 kilograms of carnallite G-1 that got, and adds up to get 13.49 kilograms of carnallites, adds Entering the fresh water total amount is 14.28 kilograms, makes decomposed solution WG16.14 kilogram, and potassium sodium is full halogen altogether Water WKN4.909 kilogram, 0.041 kilogram of impurity, saturated potassium chloride solution WK-16.68 kilogram.
Namely adopt below adding halogen method from the potassium chloride saturated bittern, to analyse potassium, also with adding halogen method from potassium Sodium takes off sodium in the full bittern altogether, and reclaims potassium; This is two key technologies of the present invention. 1, converts halogen and analyse potassium technology: 6.68 kilograms of potassium chloride saturated bittern WK-1 and carnallite are decomposed Liquid WG23.69 kilogram is converted in crystallizer mutually, and circulates 56 hours, can be from crystallization The device bottom obtains purity and reaches 99.99%, and the crystal width reaches the dry chlorination of 0.45-1.0 millimeter Potassium Q11.20 kilogram, its potassium yield is 61.76%. Discharge simultaneously potassium chloride crystallization bittern 29.13 kilograms of WP send it into spontaneous nucleation in the natural evaporation pond, and getting the crystal width is 0.15-0.5 millimeter dry potassium chloride Q20.49 kilogram, its purity is 97.28%, and its potassium is received Rate is 24.80%, and the potassium total recovery 86.56% of full technology is discharged altogether full bittern WKN of potassium sodium 23.81 kilogram. 2, convert halogen and take off sodium technology: 28.72 kilograms of the potassium sodium saturated liquid WKN that will decompose the carnallite gained , convert halogen with 12.17 kilograms of carnallite stage bittern WGS, and sedimentation in the input settling tank, Supernatant liquor is carnallite point bittern WG, counts 40.06 kilograms, sodium chloride 0.83 public affairs that sink to the bottom Jin can discard. Carnallite is selected 32.51 kilograms of bittern WG send into reproduced light halogen in the bittern-mixing pool Stone is got 7.55 kilograms of WG and is sent into and convert halogen in first crystallizer and analyse potassium.
The various bittern of above-mentioned technology and the analysis data of product see Table 2:
Table 2 title KCl% NaCl% MgCl2％ H
2Low 0.10 0.35 35.22 64.33 0 liquid WS-1 bischofite of sodium light halogen 19.14 11.04 30.45 38.86 0.51 stone G-1 reproduced light halogen, 22.43 5.85 32.16 39.56 0 stone G-2 bischofites crystallization stage, the 0.09 0.30 36.73 62.88 0 bittern WS-2 carnallite of O% impurity % carnallite 19.35 16.50 28.16 34.49 1.50 G-0 is put the altogether smart potassium Q of the excessive 4.31 1.60 20.73 73.36 0 flow liquid WP of the full saturated 25.20 0.11 0.38 74.31 0 solution W K-2 crystallizers of 10.08 19.87 1.12 68.93 0 liquid WKN carnallite crystallization stage liquid, 0.21 0.48 33.90 65.41 0 WGS KCl solution, 25.29 0.38 0.03 74.31 0 WK-1 KCl of 3.23 1.88 25.44 69.45 0 bittern WG potassium sodium199.99 0.02 0.001 0.30 0 smart potassium Q297.94 0.08 0.97 1.01 0 crystal seed 95.99 0.07 0.64 3.30 0
Adding halogen method of the present invention takes off sodium and analyses potassium high purity Process of Potassium Chloride, in the halogen temperature from-15 ° Converting halogen in-35 ℃ the scope throws the total recovery of potassium chloride great impact is arranged. Cause For, when the halogen temperature changed, the data of the various materials on the phasor simultaneously can automatic adjustable balance. The institute With the effect that the starting point of technology is to take off sodium, adopt adding halogen method to take off sodium and can obtain high potassium content The potassium chloride saturated bittern, its essence is that the carnallite point bittern that refluxes in the technology removes reproduced light During halogen stone, gained be a kind of low-sodium carnalite, the chlorine that such carnallite is produced after decomposing Changing the potassium saturated solution also is to hang down sodium, high purity potassium chloride after selecting bittern to convert halogen with carnallite Then must have very high potassium chloride total recovery.
The shape of the crystalline solid of product K Cl can manual control with size, namely after converting halogen Add needle-like, slab-like crystal seed in the liquid phase, after in crystallizer, circulating certain hour, Can make the crystalline product of KCl of needle-like or slab-like, the width of crystallization generally 0.45-0.9mm maximum can reach 1.0-1.5mm, length can reach 5mm.
The production cost of this big crystalline product is not high, and purity is very high, removes as SILVER REAGENT , outside technical grade uses; Can be used for equally agricultural as the senior chlorine potassium fertilizer that contains, because its branch The property of loosing is good, and it is few to carry the magnesium sodium impurity secretly, can bring benefit for the salinization of soil that slows down soil.
Adopt Process of Potassium Chloride processed of the present invention, with the method phase of in the past various preparing potassium chlorides Ratio has obvious advantage, only needs a small amount of fresh water to participate in decomposing low sodium light halogen such as this law Stone, and avoided removing to process the nature carnallite with a large amount of fresh water in the past; This law is in crystallization Convert halogen or add a small amount of low-sodium carnalite with two kinds of bittern in the device and analyse potassium, not directly to crystallizer In but fresh water, and the cold crystallization method will be taken off mother liquid of sodium with fresh water, carnallite, circulation and added simultaneously Enter in the crystallizer, can only make like this powder potassium chloride of technical grade; This law adopts adding halogen method After taking off sodium, the saturated potassium chloride solution of analysing behind the potassium of gained can directly enter the natural evaporation pond In separate out content by natural evaporation and reach large crystal products potassium chloride more than 97%, thereby reduce Energy consumption, improved the total recovery of potassium, and this effect is to be beyond one's reach in other method When this law is analysed potassium at crystallizer, can control product chlorine under the condition cheaply artificially Change the size of potassium crystal, this also is impossible for other method. In a word, because originally The potassium yield height of method, production cost are lower than other the whole bag of tricks at present, and produce the worker It is also quite simple to plant, and wherein contains natural evaporation pond part, is specially adapted to China Cha Er sweat The drought of Salt Lake Area, the highlands that evaporation capacity is big produce high-grade big knot Brilliant potassium chloride can create higher economy and hand over benefit under the condition of saving a large amount of investment of productions With social benefit.
To make detailed elaboration: embodiment 1 to system potassium technology of the present invention by embodiment below: according under the normal pressure, 20 ℃ K
+, Na
+, Mg
++∥ Cl
--H
2Relevant point in the KCl crystallizing field of O quaternary salt-water system phasor, calculate various participation reaction raw material answer add-on.Convert halogen with reference to the KCl crystallisation stage saturated bittern WK-143 kilogram of accompanying drawing 5 23.9 ° of Be ' that adding has simultaneously been measured in first crystallizer and the carnallitite crystallisation stage saturated bittern WG144 kilogram of 31 ° of Be ', again after circulating 56 hours, carry out solid-liquid separation, the mother liquor of 28.5 ° of Be ' of gained enters for 184.03 kilograms and adds carnallitite G7.75 kilogram in second crystallizer, after circulating 56 hours, be solid-liquid separation, get the full altogether 189.77 kilograms of dischargings of bittern WKN of potassium sodium.The wet KCl of gained is through with 0.99 kilogram of washing of the KCl crystallisation stage saturated bittern WK-1 of 20 ° of Be ' meter after drying from first crystallizer, promptly gets the big xln KCl Q of 99.99% analytical pure level
12.97 kilogram, the yield of its potassium is 58%, and washings returns to and analyses potassium in first crystallizer again.From second crystallizer, make wet KCl2.01 kilogram, after washing drying purity is 97.0% crystalloid KCl Q
21.94 kilogram, the yield of its potassium is 19.86%.Product Repone K crystalline width is generally at 0.45-1.0mm, and maximum can reach 1.0-1.5mm, and length can reach 5mm.The total recovery of Repone K is 77.86%.Embodiment 2: make Theoretical Calculation and with reference to accompanying drawing 6 according to 20 ℃ quaternary salt-water system phasor, take 22.48 kilograms of the full altogether bittern WKN of potassium sodium, Repone K saturated bittern WK-14.56 kilogram, the WK-23.42 kilogram, carnallite decomposition liquid WG adds together in first crystallizer for 7.72 kilograms and converts halogen, add 0.45 kilogram of crystal seed simultaneously, after circulating 1 hour, can from the drain hole of crystallizer bottom, discharge slip, through separating, washing, washings returns in first crystallizer, the dry then Repone K product Q that gets
11.38 kilogram is analysed 36.76 kilograms of KCl saturated bittern WKA behind the potassium.Take 22.44 kilograms of the full altogether bittern WKN of potassium sodium, 36.76 kilograms of Repone K saturated bittern WKA, 10.96 kilograms of low-sodium carnalite G, be added to together and convert halogen in second crystallizer and analyse potassium, and after circulating 56 hours, emit slip from the crystallizer bottom, through separating, washing, its washings is that Repone K saturated bittern WK-23.42 kilogram returns in second crystallizer and analyses potassium, and the solid phase after the washing is drying to obtain product Repone K Q
21.93 kilogram.The slip of from the overflow port of second crystallizer, discharging, after settlement separate, get 68.15 kilograms of the full altogether bittern WKN of potassium sodium, the WKN22.48 kilogram sent in first crystallizer analyse potassium, other WKN sends in second crystallizer for 22.44 kilograms and analyses potassium, 23.02 kilograms of dischargings of remaining WKN, the potassium total recovery of full technology is 80.52%.Embodiment 3: make Theoretical Calculation and with reference to accompanying drawing 4 and accompanying drawing 3 according to 20 ℃ quaternary salt-water system phasor, take 12171 kilograms of 28716 kilograms of full altogether bittern WKN of potassium sodium and carnallitite stage bittern WGS, pump into simultaneously and convert the halogen groove and convert halogen and take off sodium, and flow in the settling bowl automatically, sodium-chlor is sunken at the bottom of the pond, counts heavy 826 kilograms; Simultaneously pump is got 40062 kilograms of supernatant liquids, and this clear liquid is carnallitite point bittern WG, divides to convert halogen in 7555 kilograms of adding first crystallizers getting wherein and analyse potassium; Getting remaining WG32507 kilogram again sends into and converts halogen and make carnallitite G-2 again.Embodiment 4: the quaternary salt-water system phasor according to 35 ℃ is made Theoretical Calculation, press identical operations technology with salt pan carnallitite G-010 kilogram with reference to accompanying drawing 3, add 50.87 kg of water chloromagnesite point bittern WS-1, through separate low-sodium carnalite G-19.80 kilogram, discharging contains 51.07 kilograms of sodium washing lotions; Mend 1.2 kilograms of the carnallitite G-2 of reclaiming in the carnallitite bittern-mixing pool, add 4.63 kilograms of fresh water, the decomposed solution carnallitite is selected 13.08 kilograms of bittern WG and is sent to crystallizer halogen to be converted and analyse potassium; Carnallitite decomposes the isolated solid phase in back and adds 1.56 kilograms of fresh water, dissolves, separates to such an extent that potassium sodium saturated liquid WKN sends to for 2.35 kilograms and converts halogen and take off sodium; Separating obtained solid phase is added 4.41 kilograms of fresh water dissolving clarification again, get its clear liquor and be Repone K saturated bittern WK-16.24 kilogram and send in the crystallizer halogen to be converted and analyse potassium; Take off the sodium pond and to introduce carnallitite and select 11.08 kilograms of bittern WG and also send into and convert halogen with 13.08 kilograms of aforesaid WG, WK-16.24 kilogram in the crystallizer and analyse potassium from converting halogen, after circulating 56 hours, discharge slip from the crystallizer bottom, can get KCl content through separation, washing, drying is 99.99%, and the crystal width is the large crystal products Q of 0.45-1.0MM
11.20 kilogram, its potassium yield is 61.39%; From the effusive Repone K crystallisation stage of the overflow port of crystallizer saturated bittern WP, add up to 29.16 kilograms with the separating obtained liquid phase WP of crystallizer bottom slip and send into that evaporative crystallization goes out Repone K in the spontaneous evaporation pond, its slip can get KCl content after separating drying be 97.28%, and the crystal width is the large crystal products Q of 0.15-0.5MM
20.52 kilogram, the yield of its potassium is 26.22%, and then the potassium total recovery of this technology can reach 87.61%.Embodiment 5: the quaternary salt-water system phasor according to 0 ℃ is made Theoretical Calculation, press identical operations technology with 10 kilograms of salt pan carnallitite G-0 with reference to accompanying drawing 3, add 50.865 kg of water chloromagnesite point bittern WS-1, through separate low-sodium carnalite G-19.8 kilogram, discharging contains 51.07 kilograms of sodium washing lotions, mend 1.92 kilograms of the carnallitite G-2 of reclaiming in the carnallitite bittern-mixing pool, add 14.522 kilograms of fresh water, get decomposed solution carnallitite point bittern WG14.177 kilogram, return carnallitite pond regeneration carnallitite; Potassium sodium saturated liquid WKN sends into for 4.334 kilograms and converts halogen and take off in the sodium pond, adds 10.403 kilograms of carnallitite crystallisation stage bittern WGS, makes 13.968 kilograms of new carnallitite point bittern WG, sends into the carnallitite of regenerating in the bittern-mixing pool; And isolated sodium chloride as impurity can discard for 0.769 kilogram, converts the technology that halogen takes off sodium recovery Repone K thereby finish; The Repone K saturated bittern WK-17.731 kilogram that therefrom makes is sent in the crystallizer, adding carnallitite again selects bittern WG and converts halogen for 27.059 kilograms and analyse potassium, be separable that Repone K saturated bittern WP33.608 kilogram is sent into crystallization in the Repone K spontaneous evaporation pond after flowing 56 hours, after separating drying, can get purity and be 97% Repone K Q
20.566 kilogram, the yield of its potassium is 29.22%; From crystallizer, separate to such an extent that purity is 99% macrocrystal high purity potassium chloride Q simultaneously
1,, weighing is 1.138 kilograms after drying, the yield of its potassium is that the Repone K total recovery of 58% technology is 87.22%.
Claims (4)
1, a kind of new halogen of converting takes off sodium and analyses the potassium method, be according under the normal pressure ,-15 °-+35 ℃ K
+, Na
+, Mg
++∥ Cl
--H
2Each crystallizing range of O salt-water system phasor, relevant data in the crystallization line segment, calculate various participation reaction raw material answer add-on, take off sodium then and analyse the potassium operation, it is characterized in that the full altogether bittern WKN of the potassium sodium that adopts in the work flow, its concentration be 20 ° of-31 ° of Be ' can with carnallitite crystallisation stage bittern WGS, its concentration is 33 ° of-36.5 ° of Be ', after converting halogen mutually, promptly flow into sodium salt is sunken at the bottom of the pond, its supernatant liquid is carnallitite point bittern WG, can analyse potassium and regeneration carnallitite G-2 use for converting halogen, and the sodium salt of bottom can be removed regularly, this promptly is to convert halogen to take off sodium technology;
Analyse and add 20 °-30.5 ° Be ' KCl crystallisation stage saturated bittern WK-1 that measured in first crystallizer of potassium and convert halogen the carnallitite crystallisation stage saturated bittern WGS that adds 30.5 ° of-33.0 ° of Be ' and analyse potassium, in crystallizer after circulating 56 hours, promptly carry out solid-liquid separation, mother liquid obtained is KCl crystallisation stage bittern WP, can return and go spontaneous evaporation to analyse potassium once more in the spontaneous evaporation crystallizing pond, the wet KCl of gained promptly gets high-purity macrocrystal KCl product Q of 97% through the KCl crystallisation stage saturated bittern WP washing after drying with 20 ° of Be '
2, yield is that 19-29% its washings can return in the flow process and handles; The slip of discharging from the crystallizer bottom can make KCl content and reach 99.99% large crystal products Q after separation, washing, drying
1, yield is 58-61%; The average total recovery of its potassium reaches about 77-87%.
2, the halogen of converting according to claim 1 takes off sodium and analyses the potassium method, the shape that it is characterized in that the xln of product K Cl can artificially be controlled with size, promptly once add needle-like, slab-like crystal seed in the liquid phase after converting halogen, after in crystallizer, circulating, can make the crystalline product of KCl of needle-like or slab-like, the crystalline trans D is generally at 0.45-1.0mm, and maximum can reach 1.0-1.5mm, and length can reach 5mm.
3, the halogen of converting according to claim 1 takes off sodium and analyses the potassium method, it is characterized in that converting halogen and analyse the carnallitite crystallisation stage saturated bittern WGS that potassium also can add 20 °-30.5 ° Be ' KCl crystallisation stage saturated bittern WK-1 and 30.5 ° of-33.0 ° of Be ', and carnallitite G-2 converts halogen and analyses potassium, equally in crystallizer after circulating 56 hours, promptly carry out solid-liquid separation, mother liquid obtained returning goes spontaneous evaporation to analyse potassium once more in the spontaneous nucleation pond, the wet KCl of gained promptly gets high-purity macrocrystal KCl Q of 99.99% through the KCl crystallisation stage saturated bittern washing after drying with 19.9 ° of-20 ° of Be '
1
4, the halogen of converting according to claim 1 takes off sodium and analyses the potassium method, and it is characterized in that has two kinds of methods to the recovery of potassium the KCl crystallisation stage saturated bittern WP that has small-particle Repone K that discharges from the crystallizer overflow port:
(1), in the little area of rainy steam output, WP and low-sodium carnalite G-2 dropped in second crystallizer analyse potassium, can make another part macrocrystal Repone K product Q
2
(2), in the big area of arid steam output short of rain, WP flows directly in the spontaneous evaporation pond and analyses potassium, makes another part macrocrystal Repone K product Q
2
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111124A CN1048958C (en) | 1995-07-18 | 1995-07-18 | Preparing large crystal high purity potassium chloride by adding halogen method to remove Na and isolate K. |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111124A CN1048958C (en) | 1995-07-18 | 1995-07-18 | Preparing large crystal high purity potassium chloride by adding halogen method to remove Na and isolate K. |
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| Publication Number | Publication Date |
|---|---|
| CN1127219A true CN1127219A (en) | 1996-07-24 |
| CN1048958C CN1048958C (en) | 2000-02-02 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7014832B2 (en) * | 2004-03-30 | 2006-03-21 | Council Of Scientific And Industrial Research | Simultaneous recovery of potassium chloride and KCL enriched edible salt |
| CN102874847A (en) * | 2012-10-22 | 2013-01-16 | 益盐堂（应城）健康盐制盐有限公司 | Potassium-chloride product and preparation method thereof |
| CN107954452A (en) * | 2017-12-18 | 2018-04-24 | 青海盐湖工业股份有限公司 | A kind of KCl production device mother liquor at low temperature convert halogen technology |
| CN110767272A (en) * | 2019-10-29 | 2020-02-07 | 青海盐湖工业股份有限公司 | Method for drawing water-salt system phase diagram |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3895920A (en) * | 1970-09-03 | 1975-07-22 | Donald E Garrett | Method of producing coarse potash |
-
1995
- 1995-07-18 CN CN95111124A patent/CN1048958C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7014832B2 (en) * | 2004-03-30 | 2006-03-21 | Council Of Scientific And Industrial Research | Simultaneous recovery of potassium chloride and KCL enriched edible salt |
| CN102874847A (en) * | 2012-10-22 | 2013-01-16 | 益盐堂（应城）健康盐制盐有限公司 | Potassium-chloride product and preparation method thereof |
| CN102874847B (en) * | 2012-10-22 | 2014-06-04 | 益盐堂（应城）健康盐制盐有限公司 | Potassium-chloride product and preparation method thereof |
| CN107954452A (en) * | 2017-12-18 | 2018-04-24 | 青海盐湖工业股份有限公司 | A kind of KCl production device mother liquor at low temperature convert halogen technology |
| CN110767272A (en) * | 2019-10-29 | 2020-02-07 | 青海盐湖工业股份有限公司 | Method for drawing water-salt system phase diagram |
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| Publication number | Publication date |
|---|---|
| CN1048958C (en) | 2000-02-02 |
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