CN1275531A - Method for directly obtaining low-sodium fine carnallitite - Google Patents
Method for directly obtaining low-sodium fine carnallitite Download PDFInfo
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- CN1275531A CN1275531A CN 00112360 CN00112360A CN1275531A CN 1275531 A CN1275531 A CN 1275531A CN 00112360 CN00112360 CN 00112360 CN 00112360 A CN00112360 A CN 00112360A CN 1275531 A CN1275531 A CN 1275531A
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Abstract
The direct preparation method of low-sodium high-quality carnallite is characterized by adopting the following steps: adding solid bischofite into the bittern in crystallization stage of carnallite at normal temp. and under normal pressure, stirring and using Baum'e degree measurement to regulate the quantity change of charging materials, and when it is reached to Baume' degree requirement, discharging and making solid-liquid separation. Its obtained solid phase is the invented product low-sodium high-quality carnallite, and the discharged liquid phase and overflow liquor are combined into old bittern, and the old bittern can be remate into solid bischofite for circulating use. Said invented carnallite is high in yield, simple in production process, and the finished carnallite can be used to produce high-pure potassium chloride.
Description
The present invention relates to a kind of preparation method of making potassium raw material carnallitite in the inorganic chemistry.
China often produces carnallitite by the mother liquid evaporation after the salt manufacturing in coastal salt district at present, and the bittern of Qinghai Chaerhan salt lakes needs to produce carnallitite through the method that shine on the beach, salt pan.Repone K is produced by decomposing carnallitite.The quality of carnallitite quality has very big influence to the yield and the quality of the Repone K produced.Usually the quality of confirming carnallitite is adding fresh water in carnallitite, makes sodium-chlor that magnesium chloride and carnallitite in the carnallitite carry secretly all after the dissolving, and the content of seeing Repone K in the solid phase of remainder decides the good and bad quality of this carnallitite.The content of Repone K≤20% in the solid phase of remainder can claim this raw material carnallitite to be called high almeraite; The content of Repone K is 20-50% in the solid phase of remainder, and its raw material carnallitite is called the salt pan carnallitite; The content of Repone K is 50-65% in the solid phase of remainder, and its raw material carnallitite is called low-sodium carnalite; The content of Repone K is 65-80% in the remaining solid phase, and its raw material carnallitite is called the high-quality carnallitite.
China's Qinghai Chaerhan salt lakes has adopted new technology now, promptly is that adding halogen method is produced carnallitite, and this method is to join mutually with the old halogen of separating out carnallitite with carnallitite crystallisation stage bittern to convert, and makes the composition point Y that converts back bittern mutually, sees accompanying drawing 1; Bittern that this Y is ordered needs further dehydration by evaporation to the WS point, and carnallitite is separated out fully, thisly converts that isolated carnallitite promptly is a low-sodium carnalite after the halogen, and its yield is 35-40%; Y selects bittern, and to shine what make crude salt Tanaka be high almeraite, and up to the present this high almeraite does not still have more suitable treatment process.And the maximum characteristics of converting halogen a large amount of Y point bittern that is outputs.
This shows the adding halogen method of converting with liquid and liquid ginseng, will inevitably a large amount of Y point bittern of output, need evaporation slough a large amount of water, carnallitite is separated out fully, make Repone K obtain recovery.Because the concentration ratio carnallitite point bittern of Y point bittern is big, so the evaporation of water rate greatly reduces, then must build more large-area salt pan, this not only makes the corresponding raising of cost in salt pan, and the yield of its low-sodium carnalite also only is 35-40%.Therefore, though utilize adding halogen method can obtain low-sodium carnalite, the production cost of its carnallitite is very high, and technical requirements height, limitation are big, and the technical problem of existence is many.Make adding halogen method only rest on the small-scale production stage, be difficult to further promote the use of.
But, up to the present, also do not have better method directly to produce low-sodium carnalite, high-quality carnallitite.
Owing to isolate the bittern behind the carnallitite, be called old halogen, old halogen is evaporated to does that can to make the solid water chloromagnesite be sophisticated technology, this product is that a kind of magnesium chloride hexahydrate xln that is entrained with a small amount of Repone K is a good raw material of producing MAGNESIUM METAL and magnesium compound, but the bischofite utility value is not high, and the trucking costs of outwards transporting from the Northwest is also very high, be deposited in the mining area and can destroy the quality of mining area mineral products again, so a large amount of old halogen is discharged in the regulation discharge region outside the mining area, forms a large amount of solid water chloromagnesites through spontaneous evaporation.This solid water chlorine stone as waste material be if can be used and produce carnallitite and extract Repone K, and non-be a kind of good method of killing two birds with one stone.
The purpose of this invention is to provide a kind of method that can directly produce low sodium, high-quality carnallitite, it is that the method that adopts the degree Beaume specific gravity hydrometer to measure the bittern degree Beaume is at normal temperatures and pressures controlled quantitative solid water chloromagnesite and joined among the quantitative carnallitite crystallisation stage bittern, this bittern also can be described as carnallitite point bittern, after regularly stirring, promptly carry out liquid-solid separation, the solid phase of its gained promptly is low-sodium carnalite, high-quality carnallitite, and the liquid phase of discharge is old halogen.The carnallitite yield of this method is up to about 95%, so the utilization ratio height of its potassium, the waste liquid of generation are few, changed the production technique of original salt lake Repone K, the purity of Repone K product is greatly improved, and being the price of 90% Repone K than common content, the price of high purity potassium chloride exceeds 2 times, so its economic benefit and social benefit are higher.
The present invention implements like this:
Can directly produce the method for high-quality carnallitite, it is that the method that adopts the degree Beaume specific gravity hydrometer to measure the bittern degree Beaume is at normal temperatures and pressures controlled quantitative solid water chloromagnesite and joined in the quantitative carnallitite point bittern, after regularly stirring, promptly carry out liquid-solid separation, the solid phase of its gained promptly is low-sodium carnalite, high-quality carnallitite, and the liquid phase of discharge is old halogen.The carnallitite yield of this method is up to about 95%, this method can also be reclaimed the Repone K that was entrained in originally in the bischofite, so be that a kind of technology is simple, potassium rate of recovery height, the method for producing low-sodium carnalite, high-quality carnallitite that the carnallitite yield is high.
Its theoretical foundation is according to the K in the Soviet Union, the Moscow nineteen fifty version " inorganic salt solubleness handbook "
+, Na
+, Mg
++∥ Cl
--H
2The evaporation typical curve of 25 ℃ of isothermal evaporation phasors of O quaternary system is seen accompanying drawing 1.The carnallitite point bittern of evaporation curve should be at the WG of phasor point, and main solid phase is carnallitite and sodium-chlor in this bittern.And the WS point is a bischofite saturation point bittern, also is the starting point that is commonly referred to old halogen.Curve WG-WS is that carnallitite point bittern WG is evaporated to bischofite ctystallizing point bittern WS, the i.e. evaporation curve of carnallitite crystallisation stage bittern.On the right side of WG-WS curve is carnallitite KClMgCl
26H
2The crystallizing field of O, and the left side is the crystallizing field of NaCl salt.So can think that magnesium chloride is undersaturated on this WG-WS evaporation curve, move to the WS point in order to make WG point bittern, the normally used method that is dehydration by evaporation improves salt concn in the bittern is produced carnallitite.And be to adopt the method that in this WG point bittern, adds the solid water chloromagnesite now, shifting to the whole process that WS orders from the WG point is the process of adding solid bischofite.The content of magnesium chloride of visible carnallitite point bittern WG is 82% from phasor, still unsaturation.In carnallitite point bittern WG, add bischofite so, this bischofite must decompose in bittern, the concentration of the magnesium chloride of carnallitite point bittern WG is raise, bittern WG constantly moves to the WS point when raising, because carnallitite point bittern WG is a kind of be potassium, sodium, three kinds of saturated bittern of muriate of magnesium, for the material in the bittern is averaged out, can only when adding magnesium chloride, separate out carnallitite and sodium-chlor, till arriving the WS point, WS point bittern promptly is bischofite crystallisation stage bittern, promptly old halogen.WS point on the curve moves up again, and its crystallisate of separating out can only be a bischofite.Adding the solid water chloromagnesite at whole carnallitite point bittern WG shifts in the process of WS point bittern the bittern point, adopt the degree Beaume specific gravity hydrometer to measure the proportion of bittern, its degree Beaume is all the time between 36 ° of-36.5 ° of Be ', thereby proved that this moment, the dissolving material in bittern was to keep equilibrated, also met the processing requirement of directly producing low-sodium carnalite, high-quality carnallitite.
Can directly produce the method for high-quality carnallitite, be will be originally to dry in the solid water chloromagnesite QS that forms and salt Tanaka's the carnallitite carnallitite point bittern WG adding crystallizer for the mother liquor of discharging, their feed ratio is that the degree Beaume proportion of reaction mother liquor is as requested controlled; Continuously stirring 20-40 minute, can emit slip from the crystallizer bottom and carry out centrifugation, separating obtained solid promptly is low-sodium carnalite, high-quality carnallitite QG.And the mother liquor of discharging from the overflow port on crystallizer top with centrifugation and mother liquor merge into old halogen WS, can discharge or utilization again.The yield of its finished product carnallitite is about 95%.
The actually operating that can directly produce the method for high-quality carnallitite is such:
(1) sample is asked for the weight that should add the solid water chloromagnesite in the carnallitite point bittern weight of regulation:
Get a kilogram carnallitite point bittern, join in the crystallizer of one 4.5 liter capacity, take by weighing solid water chloromagnesite 1/2a kilogram earlier and join in the crystallizer, begin to stir.Put into a degree Beaume specific gravity hydrometer in the mother liquor of the settling section on crystallizer top, the degree Beaume that records mother liquor this moment is less than 36 ° of Be '; Take by weighing solid water chloromagnesite a kilogram more in addition, solid water chloromagnesite with a kilogram in 60 minutes adds in the crystallizer continuously, and constantly observe the variation of the degree Beaume of its B, when the reading of B is constant, promptly promptly stop to add the solid water chloromagnesite at 36 ° of-36.5 ° of Be '; If remaining solid water chloromagnesite amount is the b kilogram, so can determine to use a kilogram carnallitite point bittern, needing to add solid water chloromagnesite amount is the 1/2a+a-b kilogram.
In order to know the quality of product carnallitite, and ask for the yield of carnallitite, it is necessary that each material is done chemical examination.Its analysis data table is as follows:
The chemical constitution table compound title KCl% NaCl% MgCl of material
2% H
2O% weight (kilogram) carnallitite point bittern WG K
WGBischofite QS K
QSOld halogen WS K
WSThe carnallitite QG K that makes
QG
(2) experimental data by sample calculates the weight 1/2a+a-b kilogram that a kilogram carnallitite point bittern should add the solid water chloromagnesite.So in the time of can extrapolating more scale operation, the feed ratio of solid water chloromagnesite and carnallitite point bittern, feed in the crystallizer of suitable capacity then by screw feeder and rotary conveyor; With water pump carnallitite is put bittern simultaneously and join in the crystallizer, after in the settling section of the top of crystallizer clarified mother liquor being arranged, can plug the degree Beaume specific gravity hydrometer in mother liquor, specifying degree Beaume is to be benchmark in the scope of 36 ° of-36.5 ° of degree the time.When degree Beaume is lower than 36 °, carnallitite can be put the control valve of bittern and open greatly, unnecessary carnallitite point bittern can be flow back in the carnallitite point bittern storage tank by Y-tube go; Point out degree Beaume when B and will then should turn down the control valve of carnallitite point bittern, more carnallitite point bittern is entered in the crystallizer near 36.5 ° of Be ' times.And in the discharge nozzle of crystallizer bottom, will constantly flow out slip, after this slip process whizzer separation, the solid phase of its gained is low-sodium carnalite, high-quality carnallitite, and effusive liquid phase merging is old halogen in liquid phase of separating and the crystallizer upflow tube, for discharging or utilization again.So can directly produce the production process of the method for low sodium, high-quality carnallitite is successive.
The calculation formula of the yield P of carnallitite:
The content that discontinuous is produced Repone K in raw material that available reality once feeds intake, the finished product calculates, and continuous production can calculate with the average KCE content of average charging capacity and raw material, finished product.Calculation formula is constant.
P＝K
QG/(K
QS+K
WG)×100％。
Can directly produce method adoptable production unit in large-scale production of low sodium, high-quality carnallitite, except that crystallizer, also steel basin, agitated pool can be arranged, settling section, overflow port are all arranged at the top of these equipment, and drain hole is all arranged at the bottom.Generally after feeding intake for the first time, stir 20-40 minute material and in production unit, can reach balance, so but continuous dosing.The clarified mother liquor of discharging from overflow port is pure old halogen, though and the slip that discharge the equipment bottom through centrifugation and mother liquor also be old halogen, but because of being entrained with impurity, be comparatively ideal so remove to shine system solid water chloromagnesite with clarified mother liquor, the solid phase of centrifugation gained is the finished product carnallitite.The finished product carnallitite yield of its large-scale production is about 95%.
Because after the method for low sodium, high-quality carnallitite can be directly produced in employing, carnallitite needn't shine system salt Tanaka again, then can transform solarization system solid water chloromagnesite usefulness into being used to shine the antiseep salt pan of making carnallitite originally, then the requirement in its salt pan reduces, and can save a large amount of salt pan maintenance costs thus.
Employing can directly be produced the method for low sodium, high-quality carnallitite and be compared with the various methods of producing carnallitite in the past, has tangible economic benefit and social benefit to be:
Do not use any assistant medicament; The solid water chloromagnesite directly dropped in the carnallitite point bittern to stir to obtain the product carnallitite, so its production technique is the simplest at present; The yield of its carnallitite exceeds more than one times than existing adding halogen method; The Repone K of carrying secretly in the raw water chloromagnesite can be reclaimed together; Cancelled the program that removes sodium-chlor in the usual method; Cost height, carnallitite crystallization salt pan that difficulty is high have been cancelled; Make salt lake Repone K produce high purity potassium chloride under the constant condition of production cost, its price is that 90% price exceeds 2 times than common production KCE content.
With embodiment the method that can directly produce low sodium, high-quality carnallitite is done detailed elaboration below with reference to accompanying drawings.
Accompanying drawing 1 is the K that can directly produce in " the inorganic salt solubleness handbook " that the method for low sodium, high-quality carnallitite adopts
+, Na
+, Mg
++∥ Cl
--H
225 ℃ of isothermal evaporation phasors of O quaternary system;
Accompanying drawing 2 is the process flow diagrams that can directly produce the method for low sodium, high-quality carnallitite.
Embodiment 1:
(1) sample is asked for the weight that should add the solid water chloromagnesite in the carnallitite point bittern weight of regulation:
Get 3 kilograms of carnallitite point bittern WG, join in the crystallizer 3 of one 4.5 liter capacity, take by weighing solid water chloromagnesite QS earlier and join in the crystallizer 3 for 1.5 kilograms, begin to stir with agitator 4.Put into a degree Beaume specific gravity hydrometer 10 in the mother liquor of the settling section on crystallizer 3 tops, the degree Beaume that records mother liquor this moment is less than 36 ° of Be '; Take by weighing 3 kilograms of solid water chloromagnesite QS more in addition, in 60 minutes, 3 kilograms solid water chloromagnesite is added in the crystallizer 3 continuously, and constantly observe the variation of the degree Beaume of its B 10, when the reading of degree Beaume fixes on 36.2 ° of Be ' and no longer changes, promptly stop to add solid water chloromagnesite QS; Its remaining solid water chloromagnesite amount QS is 1.81 kilograms, so can determine to use 3 kilograms of carnallitite point bittern WG, needing to add solid water chloromagnesite QS amount is 2.69 kilograms.
In order to know the quality of product carnallitite, and ask for the yield of carnallitite, it is necessary that each material is done chemical examination.Its analysis data table is as follows:
The chemical constitution table compound title KCl% NaCl % MgCl of material
2% H
2O% weight (kilogram) carnallitite is selected the carnallitite QG 24.21 3.52 33.19 39.08 5.49 that bittern WG 3.34 2.16 25.5 69.00 23 bischofite QS 3.13 2.68 44.13 50.06 20.62 old halogen WS 0.10 0.35 35.15 64.40 37.5 make
(2) experimental data by sample calculates 2.69 kilograms of the weight that 3 kilograms of carnallitite point bittern should add the solid water chloromagnesite.The feed ratio of carnallitite point bittern and solid water chloromagnesite when calculating again for production, so with water pump 6 carnallitite being put 23 kilograms of bittern WG joins in the crystallizer 3, belt by screw feeder 1 and rotary conveyor 2 drops into 20.62 kilograms of solid water chloromagnesite QS in the crystallizer 3 of suitable capacity, start agitator 4 and stirred 20-40 minute.After in the settling section of the top of crystallizer 3 clarified mother liquor being arranged, in mother liquor, plug degree Beaume specific gravity hydrometer 10, specifying degree Beaume is that 36.2 ° of Be ' times are benchmark, when degree Beaume is lower than 36.2 ° of Be ' times, carnallitite is put the control valve 8 of bittern WG and opened greatly, unnecessary carnallitite point bittern WG can flow back in the carnallitite point bittern WG storage tank by Y-tube 7 and go; Point out degree Beaume when B 10 and will then should turn down the control valve 8 of carnallitite point bittern near 36.2 ° of Be ' times.And after in the discharge nozzle of crystallizer bottom, will constantly flowing out 5 separation of slip process whizzer, the solid phase of its gained is 5.49 kilograms of low-sodium carnalite, high-quality carnallitite QG, and effusive liquid phase merging is 37.5 kilograms of old halogen WS in liquid phase of separating and the upflow tube 9.
The yield P of carnallitite determines:
P＝K
QG/(K
QS+K
WG)×100％
＝24.21×5.49/(3.13×20.62+3.34×23)×100％
＝132.91/(64.54+76.82)×100％
＝132.91/141.36
＝94.02％
By above operation, 23 kilograms of carnallitite point bittern WG are put into crystallizer 3, add 20.62 kilograms of solid water chloromagnesite WS continuously,, emit slip and separate 5.49 kilograms of the carnallitite QG that can get after 35 minutes with agitator 4 stirrings through whizzer 5; And the effusive liquid phase merging of liquid phase of separating and upflow tube is 37.5 kilograms of old halogen.The yield 94.02% of its carnallitite.
Embodiment 2:
(1) sample is asked for the weight that should add the solid water chloromagnesite in the carnallitite point bittern weight of regulation:
Get 3 kilograms of carnallitite point bittern, join in the crystallizer 3 of one 4.5 liter capacity, take by weighing the solid water chloromagnesite earlier and join in the crystallizer 3 for 1.5 kilograms, begin to stir.Put into a degree Beaume specific gravity hydrometer 10 in the mother liquor of the settling section on crystallizer 3 tops, the degree Beaume that records mother liquor this moment is less than 36 ° of Be '; Take by weighing 3 kilograms of solid water chloromagnesites more in addition, in 60 minutes, 3 kilograms solid water chloromagnesite is added in the crystallizer 3 continuously, and constantly observe the variation of the degree Beaume of its B 10, when the reading of B is constant, promptly, promptly stop to add the solid water chloromagnesite at 36.2 ° of Be '; Its remaining solid water chloromagnesite amount is 1.81 kilograms, so can determine to use 3 kilograms of carnallitite point bittern, needing to add solid water chloromagnesite amount is 2.69 kilograms.
In order to know the quality of product carnallitite, and ask for the yield of carnallitite, it is necessary that each material is done chemical examination.Its analysis data table is as follows:
The chemical constitution table compound title KCl% NaCl% MgCl of material
2% H
2O% weight (kilogram) carnallitite is selected the carnallitite QG 22.75 6.18 32.16 38.91 4.5 that bittern WG 2.82 1.68 26.05 69.45 21.5 bischofite QS 3.13 2.68 44.13 50.06 15 old halogen WS 0.10 0.35 34.30 65.25 38.6 make
(2) experimental data by sample calculates 2.093 kilograms of the weight that 3 kilograms of carnallitite point bittern should add the solid water chloromagnesite.Join in the crystallizer 3 so carnallitite is put 23 kilograms of bittern WG, under stirring, in the crystallizer 3 of suitable capacity, drop into 20.62 kilograms of solid water chloromagnesite WS by screw feeder 1 and rotary conveyor 2 with agitator 4 with water pump 6.After in the settling section of the top of crystallizer 3 clarified mother liquor being arranged, in mother liquor, plug degree Beaume specific gravity hydrometer 10, specifying degree Beaume is that 36.2 ° of Be ' times are benchmark, when degree Beaume is lower than 36.2 ° of Be ' times, carnallitite is put the control valve 8 of bittern WG and opened greatly, unnecessary carnallitite point bittern WG can flow back in the carnallitite point bittern WG storage tank by Y-tube 7 and go; Point out degree Beaume when B 10 and will then should turn down the control valve 8 of carnallitite point bittern near 36.2 ° of Be ' times.And in the discharge nozzle of crystallizer 3 bottoms, will constantly flow out slip, after these slip process whizzer 5 separation, the solid phase of its gained is 5.45 kilograms of low-sodium carnalite, high-quality carnallitite QG, and liquid phase of separating and overflowing liquid merging are 37.10 kilograms of old halogen WS.
The yield P of carnallitite determines:
P＝K
QG/(K
QS+K
WG)×100％
＝24.21×5.45/(3.13×20.62+3.34×23)×100％
＝133.03/(64.54+76.82)×100％
＝133.03/141.36×100％
＝94.11％
By above operation, be that 23 kilograms of carnallitite point bittern WG are put into crystallizer 3, under the continuous stirring of agitator 4, add 20.62 kilograms of solid water chloromagnesite WS continuously, stir after 35 minutes, emit slip and separate 5.45 kilograms of the carnallitite QG that can get through whizzer 5; And liquid phase of separating and overflowing liquid are merged into 37.1 kilograms of old halogen WS.The yield 94.11% of its carnallitite.
Embodiment 3:
(1) sample is asked for the weight that should add the solid water chloromagnesite in the carnallitite point bittern weight of regulation:
Get 3 kilograms of carnallitite point bittern, join in the crystallizer 3 of one 4.5 liter capacity, take by weighing the solid water chloromagnesite earlier and join in the crystallizer 3 for 1.5 kilograms, begin to stir with agitator 4.Put into a degree Beaume specific gravity hydrometer 10 in the mother liquor of the settling section on crystallizer 3 tops, the degree Beaume that records mother liquor this moment is less than 36 ° of Be '; Take by weighing 3 kilograms of solid water chloromagnesites more in addition, in 60 minutes, 3 kilograms solid water chloromagnesite is added in the crystallizer 3 continuously, and constantly observe the variation of the degree Beaume of its B 10, when the reading of B is constant, promptly, promptly stop to add the solid water chloromagnesite at 36.1 ° of Be '; Its remaining solid water chloromagnesite amount is 2.41 kilograms, so can determine to use 3 kilograms of carnallitite point bittern, needing to add solid water chloromagnesite amount is 2.093 kilograms.
In order to know the quality of product carnallitite, and ask for the yield of carnallitite, it is necessary that each material is done chemical examination.Its analysis data table is as follows:
The chemical constitution table compound title KCl% NaCl% MgCl of material
2% H
2O% weight (kilogram) carnallitite is selected the carnallitite QG 22.75 6.18 32.16 38.91 4.5 that bittern WG 2.82 1.68 26.05 69.45 21.5 bischofite QS 3.13 2.68 44.13 50.06 15.0 old halogen WS 0.10 0.35 34.30 65.25 38.60 make
(2) experimental data by sample calculates 2.093 kilograms of the weight that 3 kilograms of carnallitite point bittern should add the solid water chloromagnesite.Join in the crystallizer 3 so carnallitite is put 21.5 kilograms of bittern WG, in the crystallizer 3 of suitable capacity, drop into 15.0 kilograms of solid water chloromagnesite WS by screw feeder 1 and rotary conveyor 2 with water pump 6.After in the settling section of the top of crystallizer 3, clarified mother liquor being arranged, in mother liquor, plug degree Beaume specific gravity hydrometer 10, specifying degree Beaume is that 36.1 ° of Be ' times are benchmark, when degree Beaume is lower than 36.1 ° of Be ' times, carnallitite is put the control valve 8 of bittern and opened greatly, unnecessary carnallitite point bittern WG can flow back in the carnallitite point bittern WG storage tank by Y-tube 7 and go; Point out degree Beaume when Beaum 10 and will then should turn down the control valve 8 of carnallitite point bittern near 36.5 ° of Be ' times.And in the discharge nozzle of crystallizer 3 bottoms, will constantly flow out slip, after these slip process whizzer 5 separation, the solid phase of its gained is 4.5 kilograms of low-sodium carnalite, high-quality carnallitites, and liquid phase of separating and upflow tube 9 effusive liquid phases merging are 38.6 kilograms of old halogen.
The yield P of carnallitite determines:
P＝K
QG/(K
QS+K
WG)×100％
＝22.75×4.5/(3.13×15.0+2.82×21.5)×100％
＝102.38/(49.14+60.63)×100％
＝102.38/107.58×100％
＝95.16％
By above operation, be that 21.5 kilograms of carnallitite point bittern WG are put into crystallizer 3, add 15.0 kilograms of solid water chloromagnesite WS continuously,, emit slip and separate after 33 minutes with agitator 4 stirrings through whizzer 5, can get 4.5 kilograms of finished product carnallitite QG; And liquid phase of separating and upflow tube 9 effusive liquid phases merging are 38.6 kilograms of old halogen WS.The yield 95.16% of its carnallitite.
Embodiment 4:
(1) sample is asked for the weight that should add the solid water chloromagnesite in the carnallitite point bittern weight of regulation:
Get 3 kilograms of carnallitite point bittern, join in the crystallizer of one 4.5 liter capacity, take by weighing the solid water chloromagnesite earlier and join in the crystallizer 3 for 1.5 kilograms, begin to stir with agitator 4.Put into a degree Beaume specific gravity hydrometer 10 in the mother liquor of the settling section on crystallizer 3 tops, the degree Beaume that records mother liquor this moment is less than 36 ° of Be '; Take by weighing 3 kilograms of solid water chloromagnesites more in addition, in 60 minutes, 3 kilograms solid water chloromagnesite is added in the crystallizer 3 continuously, and constantly observe the variation of the degree Beaume of its B 10, when the reading of degree Beaume is constant, promptly, promptly stop to add the solid water chloromagnesite at 36.35 ° of Be '; Its remaining solid water chloromagnesite amount is 2.86 kilograms, so can determine to use 3 kilograms of carnallitite point bittern, needing to add solid water chloromagnesite amount is 1.637 kilograms.
In order to know the quality of product carnallitite, and ask for the yield of carnallitite, it is necessary that each material is done chemical examination.Its analysis data table is as follows:
The chemical constitution table compound title KCl% NaCl% MgCl of material
2% H
2O% weight (kilogram) carnallitite is selected bittern WG 1.35 1.29 28.16 69.2 39.5 bischofite QS 3.13 2.68 44.13 50.06 21.55 old halogen WS 0.10 0.35 34.3 65.25 55.70 and is made carnallitite QG 22.87 5.75 32.31 39.07 5
(2) experimental data by sample calculates 1.637 kilograms of the weight that 3 kilograms of carnallitite point bittern should add the solid water chloromagnesite.Join in the crystallizer 3 so carnallitite is put 39.5 kilograms of bittern WG, in the crystallizer 3 of suitable capacity, drop into 21.55 kilograms of solid water chloromagnesite WS by screw feeder 1 and rotary conveyor 2 with water pump 6.After in the settling section of the top of crystallizer 3, clarified mother liquor being arranged, in mother liquor, plug degree Beaume specific gravity hydrometer 10, specifying degree Beaume is that 36.35 ° of Be ' times are benchmark, when degree Beaume is lower than 36.35 ° of Be ' times, carnallitite is put the control valve 8 of bittern and opened greatly, unnecessary carnallitite point bittern WG can flow back in the carnallitite point bittern WG storage tank by Y-tube 7 and go; Point out degree Beaume when Beaum 10 and will then should open the control valve 8 of big carnallitite point bittern near 36.5 ° of Be ' times.And in the discharge nozzle of crystallizer 3 bottoms, will constantly flow out slip, after these slip process whizzer 5 separation, the solid phase of its gained is 5 kilograms of low-sodium carnalite, high-quality carnallitite QG, the liquid phase of separating with merge into 55.7 kilograms of old halogen through upflow tube 9 effusive overflow mother liquors.
The yield P of carnallitite determines:
P＝K
QG/(K
QS+K
WG)×100％
＝114.35/(53.33+67.45)×100％
＝94.68％
By above operation, be that 39.5 kilograms of carnallitite point bittern WG are put into crystallizer 3, add 21.55 kilograms of solid water chloromagnesite WS continuously,, emit slip and separate after 35 minutes with agitator 4 stirrings through whizzer 5, can get 5 kilograms of finished product carnallitite QG; And the liquid phase of separating be old halogen with from upflow tube 9 effusive overflow mother liquor merge into 55.7 kilograms.The yield 94.68% of its carnallitite.
Embodiment 5:
(1) sample is asked for the weight that should add the solid water chloromagnesite in the carnallitite point bittern weight of regulation:
Get 3 kilograms of carnallitite point bittern, join in the crystallizer 3 of one 4.5 liter capacity, take by weighing the solid water chloromagnesite earlier and join in the crystallizer 3 for 1.5 kilograms, begin to stir with agitator 4.Put into a degree Beaume specific gravity hydrometer 10 in the mother liquor of the settling section on crystallizer 3 tops, the degree Beaume that records mother liquor this moment is less than 36 ° of Be '; Take by weighing 3 kilograms of solid water chloromagnesites more in addition, in 60 minutes, 3 kilograms solid water chloromagnesite is added in the crystallizer 3 continuously, and constantly observe the variation of the degree Beaume of its B, when the reading of B 10 is constant, promptly, promptly stop to add the solid water chloromagnesite at 36.45 ° of Be '; Its remaining solid water chloromagnesite amount is 2.385 kilograms, so can determine to use 3 kilograms of carnallitite point bittern, needing to add solid water chloromagnesite amount is 2.115 kilograms.
In order to know the quality of product carnallitite, and ask for the yield of carnallitite, it is necessary that each material is done chemical examination.Its analysis data table is as follows:
The chemical constitution table compound title KCl% NaCl% MgCl of material
2% H
2O% weight (kilogram) carnallitite is selected bittern WG 2.82 1.68 26.05 69.45 15.6 bischofite QS 3.13 2.68 44.13 50.06 11.0 old halogen WS 0.1 0.35 34.30 65.25 23 and is made carnallitite QG 22.74 6.27 33.91 38.86 3.35
(2) experimental data by sample calculates 2.115 kilograms of the weight that 3 kilograms of carnallitite point bittern should add the solid water chloromagnesite.Join in the crystallizer 3 so carnallitite is put 15.6 kilograms in bittern, in the crystallizer 3 of suitable capacity, drop into 11.0 kilograms of solid water chloromagnesites by screw feeder 1 and rotary conveyor 2 with water pump.After in the settling section of the top of crystallizer 3, clarified mother liquor being arranged, in mother liquor, plug degree Beaume specific gravity hydrometer 10, specifying degree Beaume is that 36.45 ° of Be ' times are benchmark, when degree Beaume is lower than 36.45 ° of Be ' times, carnallitite is put the control valve 8 of bittern and opened greatly, unnecessary carnallitite point bittern can flow back in the carnallitite point bittern storage tank by Y-tube 7 and go; Point out degree Beaume when Beaum 10 and will then should turn down the control valve 8 of carnallitite point bittern near 36.5 ° of Be ' times.And in the discharge nozzle of crystallizer 3 bottoms, will constantly flow out slip, and after this slip was separated through whizzer 5, the solid phase of its gained was 3.35 kilograms of low-sodium carnalite, high-quality carnallitites, and liquid phase of separating and overflow mother liquor are merged into 23.0 kilograms of old halogen.
The yield P of carnallitite determines:
P＝K
QG/(K
QS+K
WG)×100％
＝22.74×3.35/(3.13×11+2.86×15.6)×100％
＝76.18/78.42×100％
＝97.14％
By above operation, 15.6 kilograms of carnallitite point bittern can be put into crystallizer 3, add 11.0 kilograms of solid water chloromagnesites continuously, stir after 34 minutes, emit slip and carry out centrifugation, 3.35 kilograms of the carnallitites that can get; And the liquid phase of separating is old halogen and the overflow mother liquor is merged into 23.0 kilograms.The yield 97.14% of its carnallitite.
Embodiment 6:
The continuous production operation of large-scale production is:
(1) sample is asked for the weight that should add the solid water chloromagnesite in the carnallitite point bittern weight of regulation:
Get 3 kilograms of carnallitite point bittern, join in the crystallizer 3 of one 4.5 liter capacity, take by weighing the solid water chloromagnesite earlier and join in the crystallizer 3 for 1.5 kilograms, begin to stir with agitator 4.Put into a degree Beaume specific gravity hydrometer 10 in the mother liquor of the settling section on crystallizer 3 tops, the degree Beaume that records mother liquor this moment is less than 36 ° of Be '; Take by weighing 3 kilograms of solid water chloromagnesites more in addition, in 60 minutes, 3 kilograms solid water chloromagnesite is added in the crystallizer 3 continuously, and constantly observe the variation of the degree Beaume of its B, when the reading of B 10 is constant, promptly, promptly stop to add the solid water chloromagnesite at 36.45 ° of Be '; Its remaining solid water chloromagnesite amount is 2.385 kilograms, so can determine to use 3 kilograms of carnallitite point bittern, needing to add solid water chloromagnesite amount is 2.115 kilograms.
(2) the 3 kilograms of carnallitite point bittern of experimental data by sample should add the feed ratio that 2.115 kilograms of solid water chloromagnesites calculate production-scale carnallitite point bittern of needs and solid water chloromagnesite.Join in the crystallizer 3 so by water pump carnallitite is put bittern continuously, the solid water chloromagnesite is joined in the crystallizer 3 by screw feeder 1 and rotary conveyor 2 by this feed ratio.Stir and plug degree Beaume specific gravity hydrometer 10 in the clarified mother liquor in the settling section of the top of crystallizer 3 after 40 minutes, if specifying degree Beaume is that 36.45 ° of Be ' times are benchmark, when degree Beaume is lower than 36.45 ° of Be ' times, carnallitite is put the control valve 8 of bittern and opened greatly, unnecessary carnallitite point bittern can be flow back in the carnallitite point bittern storage tank by Y-tube 7 go; Point out degree Beaume when Beaum 10 and will then should turn down the control valve 8 of carnallitite point bittern, more carnallitite point bittern is flowed in the crystallizer near 36.5 ° of Be ' times.Open the discharge nozzle of crystallizer 3 bottoms, after constantly effusive slip separated through whizzer 5, the solid phase of its gained was low-sodium carnalite, high-quality carnallitite, and the effusive liquid phase of liquid phase of separating and upflow tube is merged into old halogen.
This moment carnallitite the determining of yield P, can calculate by the KCE content of average charging capacity and raw material, product carnallitite.
P＝K
QG/(K
QS+K
WG)×100％
General yield is all about 95%.
Claims (2)
1, can directly produce the method for low sodium, high-quality carnallitite, feature directly joins in the carnallitite crystallisation stage bittern with the solid water chloromagnesite and produces carnallitite, and its schedule of operation is:
(1) sample is asked for the weight that should add the solid water chloromagnesite in the carnallitite point bittern weight of regulation:
Get a kilogram carnallitite point bittern, join in the crystallizer (3) of one 4.5 liter capacity, taking by weighing solid water chloromagnesite 1/2a kilogram earlier joins in the crystallizer (3), begin to stir, put into a degree Beaume specific gravity hydrometer (10) in the mother liquor of the settling section on crystallizer (3) top, the degree Beaume that records mother liquor this moment is less than 36 ° of Be '; Take by weighing solid water chloromagnesite a kilogram more in addition, solid water chloromagnesite with a kilogram in 60 minutes adds in the crystallizer (3) continuously, and constantly observe the variation of the degree Beaume of its B (10), when the reading of degree Beaume is constant, promptly promptly stop to add the solid water chloromagnesite at 36 ° of-36.5 ° of Be '; If remaining solid water chloromagnesite amount is the b kilogram, so can determine to use a kilogram carnallitite point bittern, needing to add solid water chloromagnesite amount is the 1/2a+a-b kilogram;
In order to know the quality of product carnallitite, and ask for the yield of carnallitite, it is necessary that each material is done chemical examination.Its analysis data table is as follows:
The chemical constitution table compound title KCl% NaCl % MgCl of material
2% H
2O% weight (kilogram) carnallitite point bittern WG K
WGBischofite QS K
QSOld halogen WS K
WSThe carnallitite QG K that makes
QG
(2) experimental data by sample calculates the weight 1/2a+a-b kilogram that a kilogram carnallitite point bittern should add the solid water chloromagnesite, so by screw feeder (1) and rotary conveyor (2) feed in the crystallizer (3) of suitable capacity; With water pump (6) carnallitite being put bittern joins in the crystallizer (3), after in the top settling section of crystallizer (3), clarified mother liquor being arranged, in mother liquor, plug degree Beaume specific gravity hydrometer (10), specifying degree Beaume is to be benchmark in the scope of 36 ° of-36.5 ° of degree the time, when degree Beaume is lower than 36 °, carnallitite is put the control valve (8) of bittern and opened greatly, unnecessary carnallitite point bittern can flow back in the carnallitite point bittern storage tank by Y-tube (7) and go; Pointing out degree Beaume when B (10) will be near 36.5 ° of Be ' time, then should turn down the control valve (8) of carnallitite point bittern, make more carnallitite point bittern enter into crystallizer (3), after effusive slip separates through whizzer (5) in the discharge nozzle of crystallizer (3) bottom, the solid phase of its gained is low-sodium carnalite, high-quality carnallitite, and the liquid phase of separating is merged into old halogen with effusive liquid phase from upflow tube (9).
The yield P of carnallitite determines:
P＝K
QG/(K
QS+K
WG)×100％。
2, the method that can directly produce low sodium, high-quality carnallitite according to claim 1, it is characterized in that the production unit that adopts in the large-scale production has crystallizer, steel basin, agitated pool, settling section, overflow port (9) are all arranged at the top of these equipment (3), and drain hole is all arranged at the bottom; During continuous production, experimental data by sample calculates the feed ratio that needs production-scale carnallitite point bittern and solid water chloromagnesite, by water pump carnallitite being put bittern continuously by this feed ratio again joins in the crystallizer (3), by screw feeder (1) and rotary conveyor (2) the solid water chloromagnesite is joined in the crystallizer (3), stir and plug degree Beaume specific gravity hydrometer (10) after 40 minutes in the clarified mother liquor in the top settling section of crystallizer (3), the degree Beaume that appointment should be controlled is the control benchmark, when degree Beaume is lower than the benchmark degree Beaume, carnallitite is put the control valve (8) of bittern and opened greatly, unnecessary carnallitite point bittern can be flow back in the carnallitite point bittern storage tank by Y-tube (7) go; When Beaum (10) points out that degree Beaume will be near the benchmark degree Beaume, then should turn down the control valve (8) of carnallitite point bittern, more carnallitite point bittern is flowed in the crystallizer; Open the discharge nozzle of crystallizer (3) bottom simultaneously, after constantly effusive slip separated through whizzer (5), the solid phase of its gained was low-sodium carnalite, the high-quality carnallitite, the effusive liquid phase of liquid phase of separating and upflow tube is merged into old halogen, and general yield is all about 95%;
This moment carnallitite the determining of yield P, can calculate calculation formula by the average content of the Repone K of average charging capacity and raw material, product carnallitite:
P＝K
QG/(K
QS+K
WG)×100％。
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| CN00112360A CN1124981C (en) | 2000-06-22 | 2000-06-22 | Method for directly obtaining low-sodium fine carnallitite |
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|---|---|---|---|
| CN00112360A CN1124981C (en) | 2000-06-22 | 2000-06-22 | Method for directly obtaining low-sodium fine carnallitite |
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| US7014832B2 (en) * | 2004-03-30 | 2006-03-21 | Council Of Scientific And Industrial Research | Simultaneous recovery of potassium chloride and KCL enriched edible salt |
| CN1304292C (en) * | 2002-01-31 | 2007-03-14 | 科学和工业研究委员会 | Process for recovering low sodium salt from bittern |
| CN100335411C (en) * | 2005-07-30 | 2007-09-05 | 中蓝连海设计研究院 | Method of preparing low sodium carnallite by blending halogen |
| CN101462743B (en) * | 2007-12-17 | 2010-10-13 | 贵阳铝镁设计研究院 | Method for preparing low sodium low potassium content carnallite |
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| CN1025727C (en) * | 1992-03-05 | 1994-08-24 | 化学工业部化工矿山设计研究院 | Potassium chloride preparing by chloride type patassium brine |
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2000
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| CN104261431B (en) * | 2014-09-10 | 2016-03-02 | 天津长芦汉沽盐场有限责任公司 | In a kind of KCl production, carnallitite gets rid of the recoverying and utilizing method of rear liquid |
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