CN1429768A - Improved process of producing potassium chloride by halogen conversion method - Google Patents
Improved process of producing potassium chloride by halogen conversion method Download PDFInfo
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- CN1429768A CN1429768A CN 01145335 CN01145335A CN1429768A CN 1429768 A CN1429768 A CN 1429768A CN 01145335 CN01145335 CN 01145335 CN 01145335 A CN01145335 A CN 01145335A CN 1429768 A CN1429768 A CN 1429768A
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Abstract
An improved process for preparing KCl by halogen exchange method includes such procedures of halogen exchanging, evaporating, constant-temp. settling, cooling-crystallizing, decomposing and washing. Its advantage is full separation of NaCl and MgSO4.H2O as two by-products.
Description
One, technical field
The present invention relates to the Repone K production technique, relate in particular to process of producing potassium chloride by halogen conversion method and improve.
Two, background technology
Seawater is inexhaustible natural resource, and multiple first machine salt wherein is richly stored with.Salt production mainly is to be raw material with the seawater, is the energy with sun power, sticks together, drenches process such as halogen salt Tanaka through evaporation concentration, crystallization, heap and make.Mother liquor after the salt manufacturing is called " bittern ", according to the evaporation of seawater salting out law as can be known, has only a spot of calcium sulfate to follow the sodium-chlor crystallization to separate out in the process of evaporating brine, and other inorganic salts is enriched in the bittern, and the chemical constitution of bittern is as follows:
Be’ NaCl MgCl
2 MgSO
4 KCl Br
-
30 60-110 150-180 60-95 20-25 3-3.5 g/l
One ton of sea salt of every product is paid and is produced 0.8-1m
3Bittern, the annual sea salt output of China reaches 2,000 ten thousand tons, pays and produces about 1800 ten thousand steres of bittern, wherein molten 4,200,000 tons of the magnesium salts of depositing, 400,000 tons of sylvite, 5.85 ten thousand tons of bromines.Obviously, bittern is the precious resources that extracts these important industrial chemicals.Each big saltern, coastland all has the salinization factory based on the bittern comprehensive utilization of resources at present.Through production practice for many years, in bittern, extract Chemicals such as Repone K, magnesium chloride, bromine and formed sophisticated comprehensive utilization process.Wherein the Repone K product is the flagship product in this comprehensive utilization process, the quality of its state of the art and economic benefit, and the economic benefit that whole synthesis is utilized will produce very important influence.Old Repone K production technique mainly is made up of operations such as converting halogen, evaporation, insulation sedimentation, crystallisation by cooling, decomposition washing.Fig. 1 is seen in concrete technical process, and this technology was used more than 40 year in China's salinization industry, for development and national economy has also been made certain contribution.Past, the price and the labor wage of coal, water, electricity were all very low, also exempted from economically can keep down by force in planned economy period.The reform and opening-up back is under the impact of market economy flood tide, and price is constantly adjusted, and the personality of coal, water, electricity and wage for workmen etc. adjust upward significantly, and old production technique has been difficult to bear, and the situation of heavy losses has appearred in the production of Repone K.The production cost of Repone K per ton is more than 2000 yuan in recent years, and selling price is only about 1200 yuan/ton.That produces is also just many more thanks to decreasing more.Some salinization factories all alleviate the degree of Repone K loss with the profit of magnesium chloride and bromine two products now, but this does not reverse the big situation of the whole loss of salt chemical engineering.Obviously, this situation mainly causes owing to the outmoded backwardness of Repone K production technology.Each salinization factory has difficulty in taking a step at present, and the improvement of old technology is imminent.The subject matter that the old technology of producing potassium chloride by halogen conversion method exists is as follows:
1. energy consumption is too high: one ton of Repone K of every production, need from bittern, to evaporate 25 tons water approximately, and coal consumption reaches more than 4 tons, and power consumption reaches degree more than 900, and only the coal electricity charge of Xiao Haoing just reach 1350 yuan of/ton potassium.
2. bittern comprehensive utilization of resources rate is low, is embodied in:
(1) extraction yield of KCl only reaches 60-70%;
(2) one ton of Repone K of every product will be paid the high temp. salt that produces the 8-10 ton (i.e. NaCl that crystallization is separated out in evaporative process and MgSO in the production process
4H
2The O by product) Chemical Composition of high temp. salt is as follows:
KCl NaCl MgSO
4 MgCl
2
1-2％ 30-40％ 28-40％ 5-8％
Most producers melt its dissolving with seawater, are used as rudimentary fertilizer when there is the user in minority producer and sell, and economic return is very limited.The Repone K loss of only carrying secretly in the high temp. salt just accounts for more than 10% of potassium total losses.In addition, in the bittern evaporation concentration process, to evaporate a large amount of moisture content, NaCl that thereupon separates out and MgSO
4H
2O mixes, owing to do not have comparatively ideal separation means, mixing salt to be difficult to use, causes the significant wastage of resource, and environment is also polluted.
3. technical process is long, the idling amount is big: long flow path, equipment are many, complicated operation, power consumption height, manually many, depreciation is big.Add the demutation bittern that produces in the system as: dense halogen, decomposed solution, washings, high temp. salt reclaim liquid etc. all want retrieval system mix use undoubtedly these to turn one's head bittern be to do idling, all be the major reason that increases energy consumption and increase cost.
The salting out law of bittern high temperature evaporation is: along with its boiling point of raising of bittern concentration also in continuous rising.The concentrated situation that can reflect bittern according to the ebullioscopic situation of bittern indirectly.Because test-results showed the bittern boiling point before 116, mainly was the independent crystallization precipitation phase of NaCl.When boiling point is raised between the 116-121, be NaCl and MgSO
4H
2O two salt cocrystallizations are separated out, and its eduction rate reaches more than 80%, and remaining mainly is MgCl in mother liquor
2With KCl and a spot of MgBr.A large amount of carnallitites will be separated out in this mother liquor cooling back (to 30-40 ℃), and (molecular formula is KClMgCl
26H
2O), having minor N aCl to follow simultaneously separates out.Isolated carnallitite adds an amount of water (cry in the production and decompose washing) can be with MgCl wherein
2, NaCl and crystal water wash off, through obtaining containing pure KCl more than 90% after the centrifuge dehydration.Why retrieval systems such as dense halogen, bittern, decomposed solution, washings are converted halogen in the production? effect has 2 points, and the first is regulated the chemical constitution of bittern.Make MgCl
2/ KCl ratio prevents to have in the high temperature evaporation process other sylvite to separate out (because of MgSO more than 10
4Degree of supersaturation is bigger, be easy to bittern in potassium form the potassium complex salt crystal and separate out as K
2SO
42MgSO
4Double salt etc.), cause the loss of potassium, reduce the carnallitite productive rate; It two is to be blended into old halogen (MgCl wherein
2Dense) by Cl
-Common-ion effcet, can reduce NaCl solubleness.Therefore, some NaCl crystallization is separated out in converting the halogen process, can reduce the solid-to-liquid ratio of feed liquid in the evaporative process, helps evaporation operation.Concrete technology is summarized as follows: see Fig. 1.
(1) converts the halogen operation
(1) after bittern, dense halogen, decomposed solution, washings, high temp. salt recovery liquid etc. are squeezed into the tempering tank blending of converting halogen settling vessel top with pump by a certain percentage, and separates out a part of NaCl, control bittern usually: MgCl in old halogen=8: 2, the bittern
2/ KCl=10.
(2) (Dorr thickener) further mixes, analyses salt and solid-liquid separation in settling vessel, and the bottom obtains NaCl salt slurry (claiming sal amarum in the production), and top overflows halogen (promptly mixing halogen) clearly, uses for evaporization process.
(3) obtain Industrial Salt (thinner) as paying a product treatment behind the sal amarum slurry process whizzer dehalogenation.
(2) evaporization process
From converting the mixing halogen that the halogen operation is taken with pumping,, evaporate a large amount of moisture content through two-effect evaporation jar evaporation concentration.Make KCl and MgCl in the bittern
2Being concentrated, wherein have a large amount of NaCl crystallizations to separate out in II is imitated evaporating pot, mainly is MgSO in I is imitated jar
4H
2O and NaCl two salt crystallizations are separated out.Evaporation terminated boiling point is 128 ℃, about 36.5 ° of Be ' of the concentration of clear liquid.Complete evaporation of liquid, is sent into next insulation sedimentation operation and is carried out solid-liquid separation after temperature is reduced to 110 ℃ through the negative pressure cooler.
(3) insulation sedimentation operation
Containing a lot of solid phase crystal in the complete evaporation of liquid, mainly is NaCl and MgSO
4H
2Two kinds of crystal of O.At high temperature (about 110 ℃) carry out solid-liquid separation with complete evaporation of liquid, and this process is carried out in the insulation settling vessel.The high temp. salt slurry of heat is discharged in the bottom, and top overflows clear liquor (110 ℃, 36.5 ° of Be ').A certain proportion of normal temperature bittern is joined in the hot high temp. salt slurry, in a horizontal steel basin, carry out moltenly soaking mother liquor and the sylvite of carrying secretly, after the vacuum-type drum filter dehalogenation.Its filtrate is that high temp. salt recovery liquid retrieval system participates in converting halogen.Its filter cake is high temp. salt, normally melts with seawater. pour trench.
(4) crystallisation by cooling
The clear liquor that self-heat conserving sedimentation operation is sent here wherein mainly contains MgCl, KCl and minor N aCl, MgSO
4, MgBr
2Deng.This clear liquor will have a large amount of carnallitites (KCl MgCl after cooling
26H
2O) and minor N aCl separate out jointly.General cooling apparatus is a vacuum cyrsytalliser, air-cooled tower etc., and cooling temperature eventually is 30-40 ℃.After the cooling, carry out solid-liquid separation through the carnallitite settling vessel.The carnallitite slurry is discharged in the bottom.Top overflows the old halogen retrieval system participation of mother liquor (being old halogen or dense halogen in a production) part and converts halogen, and another part discharge production system can be used as raw material outward and extracts bromine (Br again
2), last mother liquor reconcentration, cooling obtains the solid substance magnesium chloride product.
(5) decompose washing procedure
Carnallitite slurry from refrigerating work procedure obtains carnallitite through the whizzer dehalogenation, and the mother liquor that throws away (dense halogen) returns and converts halogen, and carnallitite is discharged in the horizontal steel basin, adds the water decomposition washing with the MgCl in the carnallitite
2, NaCl and crystal water dissolve in liquid phase, mainly are KCl in the residue solid phase.Obtain product Repone K through behind the centrifuge dewatering.This operation normally secondary adds water, twice solid-liquid separation.For the first time adding water mainly is that branch is taken off the MgCl in the carnallitite
2, the mother liquid obtained decomposed solution that is called.The residue solid phase mainly is KCl and NaCl, and adding water for the second time mainly is to wash away NaCl, the mother liquid obtained washings that is called.Gained decomposed solution and washings are all wanted retrieval system to participate in and are converted halogen.
In a word, former process of producing potassium chloride by halogen conversion method technical obsolescence falls behind, and product is single.Energy consumption height, comprehensive utilization of resources rate are low, and the needs of incompatibility new situations development must carry out great technological transformation to it.The main direction of transforming should be to cut down the consumption of energy, improve the comprehensive utilization ratio of resource and improve overall economic benefits.
Three, summary of the invention
The objective of the invention is to, the improvement in addition suitable to existing process of producing potassium chloride by halogen conversion method, and provide a kind of process of producing potassium chloride by halogen conversion method to improve.
Novel process after the improvement keeps the several master operations and the operation control condition of former technology substantially, but the part process has been done great adjustment, to NaCl in the high temp. salt and MgSO
4H
2O has made high efficiency separation, and technological process has been done ingenious arrangement, after the increase small number of devices, obtains NaCl and MgSO again when obtaining the KCl product
4H
2Two products of O.
The present invention adopts following technical scheme.
Process of producing potassium chloride by halogen conversion method of the present invention improves, and comprise halogen operation, evaporization process, insulation sedimentation operation, crystallisation by cooling operation, decompose washing procedure, wherein,
(1) converts the halogen operation
(1) after bittern, dense halogen, decomposed solution, washings, high temp. salt recovery liquid etc. are squeezed into the tempering tank blending of converting halogen settling vessel top with pump by a certain percentage, and separates out a part of NaCl, control bittern usually: MgCl in old halogen=8: 2, the bittern
2/ KCl=10;
(2) (Dorr thickener) further mixes, analyses salt and solid-liquid separation in settling vessel, and the bottom obtains NaCl salt slurry (claiming sal amarum in the production), and top overflows halogen (promptly mixing halogen) clearly, uses for evaporization process;
(3) obtain Industrial Salt (thinner) as paying a product treatment behind the sal amarum slurry process whizzer dehalogenation;
(2) evaporization process
From converting the mixing halogen that the halogen operation is taken with pumping,, evaporate a large amount of moisture content through two-effect evaporation jar evaporation concentration.Make KCl and MgCl in the bittern
2Being concentrated, wherein have a large amount of NaCl crystallizations to separate out in II is imitated evaporating pot, mainly is MgSO in I is imitated jar
4H
2O and NaCl two salt crystallizations are separated out.Evaporation terminated boiling point is 128 ℃, about 36.5 ° of Be ' of the concentration of clear liquid.Complete evaporation of liquid, is sent into next insulation sedimentation operation and is carried out solid-liquid separation after temperature is reduced to 110 ℃ through the negative pressure cooler;
(3) insulation sedimentation operation
Containing a lot of solid phase crystal in the complete evaporation of liquid, mainly is NaCl and MgSO
4H
2Two kinds of crystal of O, needing at high temperature, (about 110 ℃) carry out solid-liquid separation with complete evaporation of liquid, this process is carried out in the insulation settling vessel, the high temp. salt slurry of heat is discharged in the bottom, top overflows clear liquor (110 ℃, 36.5 ° of Be '), and a certain proportion of normal temperature bittern is joined in the hot high temp. salt slurry, in a horizontal steel basin, carry out moltenly soaking mother liquor and the sylvite of carrying secretly, after the vacuum-type drum filter dehalogenation.Its filtrate is that high temp. salt recovery liquid retrieval system participates in converting halogen, and its filter cake is high temp. salt, normally melts with seawater, pours trench;
(4) crystallisation by cooling
The clear liquor that self-heat conserving sedimentation operation is sent here wherein mainly contains MgCl
2, KCl and minor N aCl, MgSO
4, MgBr
2Deng.This clear liquor will have a large amount of carnallitites (KCl MgCl after cooling
26H
2O) and minor N aCl separate out jointly.General cooling apparatus is a vacuum cyrsytalliser, air-cooled tower etc., and cooling temperature eventually is 30-40 ℃, after the cooling, carries out solid-liquid separation through the carnallitite settling vessel.The carnallitite slurry is discharged in the bottom, and top overflows the old halogen retrieval system participation of mother liquor (being old halogen or dense halogen in a production) part and converts halogen, and another part discharge production system can be used as raw material outward and extracts bromine (Br again
2), last mother liquor reconcentration, cooling obtains the solid substance magnesium chloride product;
(5) decompose washing procedure
Carnallitite slurry from refrigerating work procedure obtains carnallitite through the whizzer dehalogenation, and the mother liquor that throws away (dense halogen) returns and converts halogen, and carnallitite is discharged in the horizontal steel basin, adds the water decomposition washing with the MgCl in the carnallitite
2, NaCl and crystal water dissolve in liquid phase, mainly are KCl in the residue solid phase, obtain product Repone K through behind the centrifuge dewatering.This operation normally secondary adds water, twice solid-liquid separation.For the first time adding water mainly is that branch is taken off the MgCl in the carnallitite
2, the mother liquid obtained decomposed solution that is called.The residue solid phase mainly is KCl and NaCl, and adding water for the second time mainly is to wash away NaCl, the mother liquid obtained washings that is called.Gained decomposed solution and washings are all wanted retrieval system to participate in and are converted halogen; It is characterized in that,
The raw material bittern of (1) 30 ° of Be ' directly enters II and imitates evaporating pot, carries out vacuum-evaporation and concentrate under-0.09Mpa vacuum tightness, will have a large amount of NaCl to separate out separately in this equipment.When concentration reaches 33-34 ° of Be ' degree Beaume with pump connect salt band halogen enter together the insulation settling vessel be incubated solid-liquid separation;
(2) the insulation settling vessel is a dead front type, has only import and outlet, and the feed liquid that II is imitated in the evaporating pot is directly squeezed in this equipment with pump, and clear liquid directly enters I from the top vent pipe and imitates evaporating pot, and dense NaCl salt slurry is discharged by the bottom and entered the salt compounded of iodine production system;
(3) dense salt slurry is through the whizzer dehalogenation, it gets rid of back liquid and returns II effect evaporating pot, salt behind the dehalogenation enters horizontal steel basin, adding sodium chloride saturated solution simultaneously, to carry out agitator treating control solid-to-liquid ratio be 1: 1, squeeze into the whizzer dehalogenation of next stage then with pump again, wash back dehalogenation salt and enter ebullated dryer with worm conveyor, moisture in the salt of dry back only is 0.1-0.2%, through sieve apparatus macrobead is screened out the back and add iodine, be packaged into Kucheng's salt compounded of iodine product at last by adding the iodine machine.Also can not add iodine handles by Industrial Salt;
(4) the clear halogen that is come out by insulation solid-liquid separator top directly enters I and imitates in the evaporating pot continuation evaporation concentration.In I was imitated evaporating pot, that crystallization is separated out mainly was NaCl and MgSO
4H
2Two kinds of crystal of O.The dump temperature that I is imitated evaporating pot is 128 ℃, concentration 36.2-36.7 ° of Be '.Simultaneously by the demutation bittern that produces in the production system, as: evenly squeeze into I after old halogen (dense former halogen), decomposed solution, washings etc. mix and imitate participation evaporation concentration in the jar in converting the halogen groove;
(5) liquid (liquid-solid phase mixture) of finishing after I is imitated jar high temperature evaporation enters the insulation settling vessel after through negative pressure cooler (cooling is as for 110 ℃) and enters solid-liquid separation.The clear liquor of gained carries out crystallisation by cooling, obtains decomposing behind the carnallitite washing again and obtains product Repone K; (process of this system potassium is identical repeating no more with old technology)
(6) the high temp. salt slurry of discharging in insulation settling vessel awl bottom, enter horizontal steel basin and add 1: 1 molten back of soaking of bittern and squeeze into the vacuum-type drum filter dehalogenation with pump: the bittern of deviating from pumps into converts the halogen groove, and filter cake (mainly is NaCl and MgSO
4H
2O), be discharged into horizontal steel basin, the bittern that adds 30-60 ℃ simultaneously carries out dispersed with stirring, concentration 50-55 ° of Be '; Pump into WI-650 after stirring and bore separate (the filter screen aperture of this whizzer is 0.02-0.08mm) that blue formula whizzer carries out salt and magnesia magma; NaCl wherein is separated on screen cloth, enters horizontal steel basin and adds 50 ℃ of bitterns (1: 1) simultaneously, and the back that stirs is directly squeezed in the II effect evaporating pot with pump and reclaimed and recrystallize;
(7) magnesia magma that goes out by WI-650 whizzer screen filtration (mainly is MgSO
4H
2The rare soup compound of O) squeeze into plate-and-frame filter press with pump in the inflow dashpot and filter, its filtrate pumping into is converted the halogen groove; Filter cake enters the Flash Type moisture eliminator through transfer roller, after drying under 130 ℃ of temperature, obtains magnesium sulfate monohydrate (MgSO
4H
2O) product.
Below in conjunction with specific embodiment the improved technical characterictic of process of producing potassium chloride by halogen conversion method of the present invention is described in further detail.
Four, description of drawings
Fig. 1 is former process of producing potassium chloride by halogen conversion method general flow chart.
Fig. 2 is a process flow diagram of the present invention.
Fig. 3 is the sketch of the improved salt of the present invention, potassium, magnesium comprehensive utilization process.
Five, embodiment
Novel process after the improvement (seeing Fig. 2, shown in Figure 3)
Producing potassium chloride by halogen conversion method, product per ton will be paid and produce 8-10 ton high and tow temperature salt, and bittern is composed as follows:
KCl NaCl MgSO
4 MgCl
2
1-1.5％ 30-40％ 28-40％ 5-8％
For a long time, because sodium-chlor and magnesium sulfate monohydrate that high temperature evaporation is separated out are not easily separated, a lot of producers all have been used as trash discharge to it, though some salinization factory that produces vitriolate of tartar has taked the isolating method of spinning liquid, solved the problem of utilizing of part magnesium sulfate monohydrate, but because separating effect is not really desirable, NaCl is not well utilized again, so fail extensively to be promoted in the industry.
This programme is at producing potassium chloride by halogen conversion method, carries out under the constant substantially situation of every processing parameter.The raw material bittern that enters vapo(u)rization system is generally speaking:
KCl: NaCl: MgSO
4=1: about 4: 4
Because the extraction yield of Repone K production is 70%, sodium-chlor and magnesium sulfate monohydrate almost do not have process loss in the production process.So every production ton Repone K, theoretical production vacuum salt and magnesium sulfate monohydrate are respectively more than 5 tons.This scheme is utilized bittern evaporation salting out law, and sodium-chlor is separated out before 116 ℃, and the undersaturated condition of sal epsom takes the WI-650 whizzer to implement to separate to disperseing back high temp. salt slurry.Bore the oarse-grained sodium-chlor in blue top add bittern by 1: 1 the dilution after, pump into the II single-effect evaporator, sal epsom in the dissolved salt slurry is provided with Totally-enclosed-type thickener (φ 3000m/m H1000m/m) II effect vacuum salt simultaneously and changes thickener over to feed liquid between I effect and II effect, refined salt is discharged from boring the end.The II effect liquid that does not contain solid-phase chlorination sodium pumps into I automatically and imitates, and continues evaporation.The refined salt that discharge at the awl end behind centrifugal drying, can be used as refining vacuum salt product and comes into the market.Bore blue bottom and contain the back liquid of getting rid of of magnesium sulfate monohydrate (magnesia magma), but convection drying behind filter press, produce magnesium sulfate monohydrate, also can produce vitriolate of tartar, schoenite and magnesium sulfate heptahydrate are only produced different products and are selected different dispersion liquids for use, can both satisfy processing condition, from the situation of our test, adopt in the sodium-chlor after the WI-650 whizzer separates about sulfur acid magnesium 4-5%.And (magnesium sulfate monohydrate) solid phase sodium chloride-containing also is all about 4-5% in the magnesia magma of the blue bottom of awl.The magnesium sulfate monohydrate of quality all is feasible as the raw material of any product like this.
The raw material bittern of (1) 30 ° of Be ' directly enters II and imitates evaporating pot, carries out vacuum-evaporation and concentrate under-0.09Mpa vacuum tightness, will have a large amount of NaCl to separate out separately in this equipment.When concentration reaches 33-34 ° of Be ' degree Beaume with pump connect salt band halogen enter together the insulation settling vessel be incubated solid-liquid separation;
(2) the insulation settling vessel is a dead front type, has only import and outlet, and the feed liquid that II is imitated in the evaporating pot is directly squeezed in this equipment with pump, and clear liquid directly enters I from the top vent pipe and imitates evaporating pot, and dense NaCl salt slurry is discharged by the bottom and entered the salt compounded of iodine production system;
(3) dense salt slurry is through the whizzer dehalogenation, it gets rid of back liquid and returns II effect evaporating pot, salt behind the dehalogenation enters horizontal steel basin, adding sodium chloride saturated solution simultaneously, to carry out agitator treating control solid-to-liquid ratio be 1: 1, squeeze into the whizzer dehalogenation of next stage then with pump again, wash back dehalogenation salt and enter ebullated dryer with worm conveyor, moisture in the salt of dry back only is 0.1-0.2%, through sieve apparatus macrobead is screened out the back and add iodine, be packaged into Kucheng's salt compounded of iodine product at last by adding the iodine machine.Also can not add iodine handles by Industrial Salt;
(4) the clear halogen that is come out by insulation solid-liquid separator top directly enters I and imitates in the evaporating pot continuation evaporation concentration.In I was imitated evaporating pot, that crystallization is separated out mainly was NaCl and MgSO
4H
2Two kinds of crystal of O.The dump temperature that I is imitated evaporating pot is 128 ℃, concentration 36.2-36.7 ° of Be '.Simultaneously by the demutation bittern that produces in the production system, as: evenly squeeze into I after old halogen (dense former halogen), decomposed solution, washings etc. mix and imitate participation evaporation concentration in the jar in converting the halogen groove;
(5) liquid (liquid-solid phase mixture) of finishing after I is imitated jar high temperature evaporation enters the insulation settling vessel after through negative pressure cooler (cooling is as for 110 ℃) and enters solid-liquid separation.The clear liquor of gained carries out crystallisation by cooling, obtains decomposing behind the carnallitite washing again and obtains product Repone K; (process of this system potassium is identical repeating no more with old technology)
(6) the high temp. salt slurry of discharging in insulation settling vessel awl bottom, enter horizontal steel basin and add 1: 1 molten back of soaking of bittern and squeeze into the vacuum-type drum filter dehalogenation with pump: the bittern of deviating from pumps into converts the halogen groove, and filter cake (mainly is NaCl and MgSO
4H
2O), be discharged into horizontal steel basin, the bittern that adds 30-60 ℃ simultaneously carries out dispersed with stirring, concentration 50-55 ° of Be '; Pump into WI-650 after stirring and bore separate (the filter screen aperture of this whizzer is 0.02-0.08mm) that blue formula whizzer carries out salt and magnesia magma; NaCl wherein is separated on screen cloth, enters horizontal steel basin and adds 50 ℃ of bitterns (1: 1) simultaneously, and the back that stirs is directly squeezed in the II effect evaporating pot with pump and reclaimed and recrystallize;
(7) magnesia magma that goes out by WI-650 whizzer screen filtration (mainly is MgSO
4H
2The rare soup compound of O) squeeze into plate-and-frame filter press with pump in the inflow dashpot and filter, its filtrate pumping into is converted the halogen groove; Filter cake enters the Flash Type moisture eliminator through transfer roller, after drying under 130 ℃ of temperature, obtains magnesium sulfate monohydrate (MgSO
4H
2O) product.Technical process is as follows:
This technology improves the sodium-chlor utilization ratio in order to guarantee the vacuum salt whiteness, will convert the halogen operation and convert halogen before evaporating, and changes into from I effect evaporating pot and directly converts halogen, has simplified operation.
The innovation point of improvement project
1. select the screen cloth in suitable aperture for use, adopt WI-650 to bore blue formula whizzer, NaCl and the MgSO in the high temp. salt after disperseing
4H
2O has carried out separating efficiently.
2. will be in high temp. salt isolated NaCl return II and imitate evaporating pot and carry out washing and recycling.Obtain the vacuum salt of food grade.
3. imitate between evaporating pot and the II effect evaporating pot at I and set up the insulation solid-liquid separator, and discharge high-quality vacuum salt by its cone, the clear halogen in top directly advances I imitates jar, continues evaporation.
4. convert the halogen operation and convert halogen before, now change in I is imitated jar and convert halogen by the original II effect jar that advances.Guarantee the quality of vacuum salt.Reduce the potassium loss.
5. isolated magnesia magma in high temp. salt obtains qualified sulfuric acid monohydrate magnesium products by press filtration, drying.
6. at former producing potassium chloride by halogen conversion method, every processing parameter is constant substantially, obtains three products simultaneously promptly under the constant substantially situation of evaporated water: smart potassium, vacuum salt and magnesium sulfate monohydrate.
Economic analysis:
With the high and tow temperature salt is raw material, takes WI-650 centrifugation NaCl and MgSO
4H
2O technology has realized the coproduction of Repone K, vacuum salt, magnesium sulfate monohydrate, and for realizing the bittern comprehensive utilization of resources, it is significant to reduce the KCl production cost.It not only makes sodium-chlor, magnesium chloride and magnesium sulfate monohydrate obtain recovery, and high and tow temperature salt filter cake band loses in the production process 10% KCl, MgCl
2And Br
2Obtained recovery, made the KCl production rate of recovery be expected to reach more than 85%.Can reach more than 98.5% through washing dried vacuum salt sodium chloride-containing, can come into the market fully, and at present supply falls short of demand to magnesium sulfate monohydrate in the world market.Because this technology finishes on former technology basis, facility investment is lower, and its adding halogen method of can yet be regarded as is produced a revolution of KCl technological innovation.
Novel process after the improvement has following characteristics:
1. can suitably reduce the multiple solarization concentration of bittern, even can not shine again, the multiple crude salt that shines is converted into vacuum salt improve value-added content of product.
2. produce under the constant substantially situation of KCl technology at former adding halogen method, only needing to increase small part equipment just can increase vacuum salt and two products of magnesium sulfate monohydrate.
3.KCl yield can reach 85%, NaCl and MgSO
4Yield can reach 90%, simultaneously, MgCl
2And Br
2Yield also can be improved the entrainment loss of high temp. salt (mainly be reduce) accordingly, say that from integral body the comprehensive utilization ratio of bittern resource is improved significantly.
4. change the two kinds of products of getting back under the little situation at evaporated water, so save energy and reduce the cost significantly after improving technology.
5. reverse the passive situation of KCl manufacturing loss, by the novel process production after improving, through predesigne, one ton of KCl of every production can have a net gain 480 yuan.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, every foundation technical spirit of the present invention all still belongs in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (1)
1, a kind of process of producing potassium chloride by halogen conversion method improves, and comprise halogen operation, evaporization process, insulation sedimentation operation, crystallisation by cooling operation, decompose washing procedure, wherein,
(1) converts the halogen operation
(1) after bittern, dense halogen, decomposed solution, washings, high temp. salt recovery liquid etc. are squeezed into the tempering tank blending of converting halogen settling vessel top with pump by a certain percentage, and separates out a part of NaCl, control bittern usually: MgCl in old halogen=8: 2, the bittern
2/ KCl=10;
(2) (Dorr thickener) further mixes, analyses salt and solid-liquid separation in settling vessel, and the bottom obtains NaCl salt slurry (claiming sal amarum in the production), and top overflows halogen (promptly mixing halogen) clearly, uses for evaporization process;
(3) obtain Industrial Salt (thinner) as paying a product treatment behind the sal amarum slurry process whizzer dehalogenation;
(2) evaporization process
From converting the mixing halogen that the halogen operation is taken with pumping,, evaporate a large amount of moisture content through two-effect evaporation jar evaporation concentration.Make KCl and MgCl in the bittern
2Concentrated, wherein have a large amount of NaCl crystallizations to separate out in II is imitated evaporating pot, imitating in the jar 1 mainly is MgSO
4H
2O and NaCl two salt crystallizations are separated out.Evaporation terminated boiling point is 128 ℃, about 36.5 ° of Be ' of the concentration of clear liquid.Complete evaporation of liquid, is sent into next insulation sedimentation operation and is carried out solid-liquid separation after temperature is reduced to 110 ℃ through the negative pressure cooler;
(3) insulation sedimentation operation
Containing a lot of solid phase crystal in the complete evaporation of liquid, mainly is NaCl and MgSO
4H
2Two kinds of crystal of O, needing at high temperature, (about 110 ℃) carry out solid-liquid separation with complete evaporation of liquid, this process is carried out in the insulation settling vessel, the high temp. salt slurry of heat is discharged in the bottom, top overflows (110 ℃ of clear liquors, 36.5 ° Be '), a certain proportion of normal temperature bittern is joined in the hot high temp. salt slurry, in a horizontal steel basin, carry out molten mother liquor and the sylvite of carrying secretly that soaks, after the vacuum-type drum filter dehalogenation, its filtrate is that high temp. salt recovery liquid retrieval system participates in converting halogen, and its filter cake is high temp. salt, normally melt, pour trench with seawater;
(4) crystallisation by cooling
The clear liquor that self-heat conserving sedimentation operation is sent here wherein mainly contains MgCl
2, KCl and minor N aCl, MgSO
4, MgBr
2Deng, this clear liquor will have a large amount of carnallitites (KCl MgCl after cooling
26H
2O) and minor N aCl separate out jointly.General cooling apparatus is a vacuum cyrsytalliser, air-cooled tower etc., and cooling temperature eventually is 30-40 ℃, after the cooling, carries out solid-liquid separation through the carnallitite settling vessel.The carnallitite slurry is discharged in the bottom, and top overflows the old halogen retrieval system participation of mother liquor (being old halogen or dense halogen in a production) part and converts halogen, and another part discharge production system can be used as raw material outward and extracts bromine (Br again
2), last mother liquor reconcentration, cooling obtains the solid substance magnesium chloride product;
(5) decompose washing procedure
Carnallitite slurry from refrigerating work procedure obtains carnallitite through the whizzer dehalogenation, and the mother liquor that throws away (dense halogen) returns and converts halogen, and carnallitite is discharged in the horizontal steel basin, adds the water decomposition washing with the MgCl in the carnallitite
2, NaCl and crystal water dissolve in liquid phase, mainly are KCl in the residue solid phase, obtain product Repone K through behind the centrifuge dewatering, this operation normally secondary adds water, twice solid-liquid separation, adding water for the first time mainly is that branch is taken off the MgCl in the carnallitite
2, the mother liquid obtained decomposed solution that is called, the residue solid phase mainly is KCl and NaCl, and adding water for the second time mainly is to wash away NaCl, and the mother liquid obtained washings that is called, gained decomposed solution and washings are all wanted retrieval system to participate in and are converted halogen; It is characterized in that,
The raw material bittern of (1) 30 ° of Be ' directly enters II and imitates evaporating pot, carrying out vacuum-evaporation under-0.09Mpa vacuum tightness concentrates, in this equipment, will have a large amount of NaCl to separate out separately, when concentration reaches 33-34 ° of Be ' degree Beaume with pump connect salt band halogen enter together the insulation settling vessel be incubated solid-liquid separation;
(2) the insulation settling vessel is a dead front type, has only import and outlet, and the feed liquid that II is imitated in the evaporating pot is directly squeezed in this equipment with pump, and clear liquid directly enters I from the top vent pipe and imitates evaporating pot, and dense NaCl salt slurry is discharged by the bottom and entered the salt compounded of iodine production system;
(3) dense salt slurry is through the whizzer dehalogenation, it gets rid of back liquid and returns II effect evaporating pot, salt behind the dehalogenation enters horizontal steel basin, adding sodium chloride saturated solution simultaneously, to carry out agitator treating control solid-to-liquid ratio be 1: 1, squeeze into the whizzer dehalogenation of next stage then again with pump, wash back dehalogenation salt and enter ebullated dryer with worm conveyor, moisture in the salt of dry back only is 0.1-0.2%, through sieve apparatus macrobead is screened out the back and add iodine by adding the iodine machine, be packaged into Kucheng's salt compounded of iodine product at last, also can not add iodine and handle by Industrial Salt;
(4) the clear halogen that is come out by insulation solid-liquid separator top directly enters in the I effect evaporating pot, continues evaporation concentration, and in I was imitated evaporating pot, that crystallization is separated out mainly was NaCl and MgSO
4H
2Two kinds of crystal of O, the dump temperature that I is imitated evaporating pot is 128 ℃, concentration 36.2-36.7 ° of Be ', simultaneously by the demutation bittern that produces in the production system, as: evenly squeeze into I after old halogen (dense former halogen), decomposed solution, washings etc. mix and imitate participation evaporation concentration in the jar in converting the halogen groove;
(5) liquid (liquid-solid phase mixture) of finishing after I is imitated jar high temperature evaporation enters the insulation settling vessel after through negative pressure cooler (cooling is as for 110 ℃) and enters solid-liquid separation, the clear liquor of gained carries out crystallisation by cooling, obtains decomposing behind the carnallitite washing again and obtains product Repone K;
(6) the high temp. salt slurry of discharging in insulation settling vessel awl bottom, enter horizontal steel basin and add 1: 1 molten back of soaking of bittern and squeeze into the vacuum-type drum filter dehalogenation with pump: the bittern of deviating from pumps into converts the halogen groove, and filter cake (mainly is NaCl and MgSO
4H
2O), be discharged into horizontal steel basin, the bittern that adds 30-60 ℃ simultaneously carries out dispersed with stirring, concentration 50-55 ° of Be '; Pump into WI-650 after stirring and bore separate (the filter screen aperture of this whizzer is 0.02-0.08mm) that blue formula whizzer carries out salt and magnesia magma; NaCl wherein is separated on screen cloth, enters horizontal steel basin and adds 50 ℃ of bitterns (1: 1) simultaneously, and the back that stirs is directly squeezed in the II effect evaporating pot with pump and reclaimed and recrystallize;
(7) magnesia magma that goes out by WI-650 whizzer screen filtration (mainly is MgSO
4H
2The rare soup compound of O) squeeze into plate-and-frame filter press with pump in the inflow dashpot and filter, its filtrate pumping into is converted the halogen groove; Filter cake enters the Flash Type moisture eliminator through transfer roller, after drying under 130 ℃ of temperature, obtains magnesium sulfate monohydrate (MgSO
4H
2O) product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011453354A CN100471794C (en) | 2001-12-31 | 2001-12-31 | Improved process of producing potassium chloride by halogen conversion method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011453354A CN100471794C (en) | 2001-12-31 | 2001-12-31 | Improved process of producing potassium chloride by halogen conversion method |
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| Publication Number | Publication Date |
|---|---|
| CN1429768A true CN1429768A (en) | 2003-07-16 |
| CN100471794C CN100471794C (en) | 2009-03-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011453354A Expired - Fee Related CN100471794C (en) | 2001-12-31 | 2001-12-31 | Improved process of producing potassium chloride by halogen conversion method |
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| CN (1) | CN100471794C (en) |
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| CN101880099A (en) * | 2010-06-30 | 2010-11-10 | 宇星科技发展(深圳)有限公司 | Treatment process for oilfield water comprehensive recovery |
| CN102491373A (en) * | 2011-12-22 | 2012-06-13 | 化工部长沙设计研究院 | Method for producing potassium chloride, sodium chloride and magnesium sheet from bittern extracted from carnallite mine |
| CN103397201A (en) * | 2013-07-26 | 2013-11-20 | 中国科学院青海盐湖研究所 | Method for statically leaching and extracting potassium from polyhalite and preparing potassium sulphate |
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| CN104261431A (en) * | 2014-09-10 | 2015-01-07 | 天津长芦汉沽盐场有限责任公司 | Recycling method for carnallite post-throwing liquid in production of potassium chloride |
| CN104355325A (en) * | 2014-10-16 | 2015-02-18 | 中国中轻国际工程有限公司 | Technology for recovering washing mother liquid containing magnesium sulfate |
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| CN103397201A (en) * | 2013-07-26 | 2013-11-20 | 中国科学院青海盐湖研究所 | Method for statically leaching and extracting potassium from polyhalite and preparing potassium sulphate |
| CN103397201B (en) * | 2013-07-26 | 2014-12-17 | 中国科学院青海盐湖研究所 | Method for statically leaching and extracting potassium from polyhalite and preparing potassium sulphate |
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| CN115465874B (en) * | 2022-11-15 | 2023-03-07 | 山西大学 | Device and method for preparing micron-sized crystalline magnesium sulfate hollow tube |
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