CN103771460A - Method for preparing potassium mixed salt mine by using nitrate contained magnesium sulphate subtype bittern and potassium nitrate production - Google Patents
Method for preparing potassium mixed salt mine by using nitrate contained magnesium sulphate subtype bittern and potassium nitrate production Download PDFInfo
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Abstract
The invention relates to a method for sun-curing of potassium mixed salt mine with a higher potassium nitrate content and for producing of potassium nitrate through processes of natural evaporation, brine removing and the like by using six-element system intercrystalline bittern containing ions such as Na<+>, K<+>, Mg<2+>/Cl<->, SO4<2-> and NO3<->. The method comprises the following steps: 1, allowing magnesium sulfate subtype intercrystalline bittern to be subjected to evaporation and concentration, separating effluent salt to obtain high-sulfur bittern; 2, doping the high-sulfur bittern and potassium separating bittern at the mass ratio of 1:(0.8-1.6) to obtain a brine removing mixed solution, evaporating to separate sodium chloride from magnesium sulphate so as to obtain potassium saturated bittern; 3, evaporating the potassium saturated bittern to separate out potassium mixed salt; adopting a flotation manner to purify the potassium mixed salt to remove impurities so as to obtain flotation foam which is subjected to thermal solution to obtain a hot solution A; cooling the hot solution A, performing solid-liquid separation to obtain potassium mixed salt mine with the content of potassium nitrate being 95 percent. The method requires no magnesium removing agent, adopts the flotation technology, and has the advantages of low energy consumption, low equipment investment, less equipment corrosion, high product quality, low cost and the like.
Description
Technical field
The invention belongs to chemical industry of inorganic salt field, particularly a kind of utilization containing Na
+, K
+, Mg
2+/ Cl
-, SO
4 2-, NO
3 -isoionic six-membered system intercrystalline bittern (contain the magnesium sulfate salt lake intercrystalline bittern of nitrate, claim again containing the magnesium sulfate bittern of nitrate or the magnesium sulfate intercrystalline bittern that six-membered system contains nitrate) by spontaneous evaporation, the method converting the operations such as halogen and shine the higher potassium ores of potassium nitrate content processed, production saltpetre.
Background technology
Xinjiang is the unique area having containing saltpetre solid and liquid ore resources of China, utilizes this resource to produce saltpetre, no matter from locality or from national development, significant.In kentite stone ore and salt lake intercrystalline bittern, be rich in Na
+, K
+, Mg
2+, Cl
-, SO
4 2-, NO
3 -and iodine and the boron of trace, it can the natural high-quality saltpetre of processing, this product is in China and all belong in the world product in short supply, no matter added value and effect, more excellent than potassium sulfate, Repone K, be the rare green potash fertilizer of high-quality, belong to binary green fertilizer in short supply in the world, and be widely used in each industrial circle.
At present, solid mineral has carried out the exploitation of several years, and method is first to carry out the leaching of ore in mining area, and ted in leaching liquid salt pan, produces the work in-process that potassium nitrate content is higher after desalination---potassium mixed salt, then carry out precision work.Because solid mineral reserves reduce increasingly, so be badly in need of developing liquid ore deposit-salt lake intercrystalline bittern.In principle, the exploitation technical process in liquid ore deposit and solid mineral are substantially identical, first by liquid ore deposit by salt pan ted, desalination produces saltpetre work in-process, then carries out precision work; Due to the ratio of component solid mineral complexity in liquid ore deposit, utilize in process at actual development, the exploitation in liquid ore deposit, utilize exploitation, the utilization of difficulty much larger than solid mineral.
No matter solid mineral is molten after soaking bittern or intercrystalline bittern liquid ore deposit, in the time that work in-process-potassium mixed salt is produced in spontaneous evaporation, part K
+with Mg
2+, SO
4 2-separate out with double salt form, to K
+recovery and improve K
+added value has been brought very large difficulty, and many investigators mainly contain two kinds of ways to its solution, a kind of be using lime as demagging agent in the demagging of former halogen stage by the Mg in brine deposit
2+, SO
4 2-remove, and then by salt pan ted, desalination produces containing Mg
2+, SO
4 2-lower work in-process-potassium mixed salt, this method needs a large amount of lime, has increased undoubtedly the production cost of product, moreover, Mg
2+, SO
4 2-caSO with lime reaction generation
4and Mg (OH)
2to be difficult to recycle, and external in a large number for a long time, certainly will cause the pollution of environment, and the sodium-chlor that separate out in salt pan also pollutes by calcium sulfate, limit the use value of byproduct sodium-chlor.Another be with saltcake as demagging agent by the Mg in brine deposit
2+, SO
4 2-remove, specifically former halogen adds saltcake again by high temperature evaporation, separates out vanthoffite and vanthoffite is removed Mg
2+, SO
4 2-; This method needs outsourcing saltcake, moreover high temperature evaporation also needs power consumption, has increased the cost of product, and equipment corrosion is serious, and facility investment strengthens, and is unfavorable for the promotion and application of this technique.
Summary of the invention
The object of the invention is to propose a kind ofly can effectively solve the magnesium sulfate intercrystalline bittern that six-membered system contains nitrate, conventional spontaneous evaporation, shines Mg in the potassium ores of system
2+, SO
4 2-the problem that content is too high, by converting halogen, segmentation is analysed salt, produced containing Mg
2+, SO
4 2-the work in-process that content is lower---the method for potassium mixed salt, then produces technical grade saltpetre, byproduct magnesium sulfate with this potassium mixed salt.
Utilize the method for producing potassium ores containing the magnesium sulfate bittern of nitrate, comprise the following steps:
1. the magnesium sulfate intercrystalline bittern that six-membered system is contained to nitrate, by evaporation concentration, is separated out abraum salt, K in bittern
+when content (mass ratio) is 2.0%～3.2%, separate abraum salt, obtain high-sulfur bittern;
2. convert halogen: by high-sulfur bittern: analyse potassium bittern (mass ratio)=1:0.8～1.6 and mix to such an extent that convert halogen mixed solution, then spontaneous evaporation, precipitated sodium chloride and magnesium sulfate, to K in bittern
+content (mass percent) is 3.2%～3.5%, Mg
2+when content (mass percent) is 5.0%～5.5%, separate sodium-chlor and magnesium sulfate, obtain potassium saturated bittern;
3. by the evaporation of potassium saturated bittern, solid is separated out, K in bittern
+content (mass ratio) is 2.0%～2.5%, Mg content (mass ratio) is while being 5.0%～7.5%, point isolated solid and remaining liq, and solid is potassium mixed salt, remaining liq is for analysing potassium mother liquor.
onstate and utilize the method for producing potassium ores containing the magnesium sulfate bittern of nitrate: described intercrystalline bittern is in sodium salt field evaporation concentration; Described high potassium bittern imports equalizing tank, is blended into and analyses potassium bittern, spontaneous evaporation, and precipitated sodium chloride and magnesium sulfate, obtain potassium saturated bittern; Described potassium saturated bittern is imported into the pond spontaneous evaporation of potassium mixed salt and analyses potassium.
onstate the method for producing potassium ores containing the magnesium sulfate bittern of nitrate of utilizing: described in analyse potassium bittern for analysing potassium mother liquor, or make as follows analyse potassium bittern:
Get magnesium sulfate intercrystalline bittern spontaneous evaporation that six-membered system contains nitrate to the bittern of liquid phase containing potassium 2%～2.4%, the freezing 48h that is no less than below-5 ℃, then solid-liquid separation, separating obtained liquid is for freezing bittern after nitre; After freezing nitre, bittern evaporation is concentrated, is evaporated to liquid phase containing potassium 3.6%～3.9%, Mg
2+content (mass percent) is 4.2%～4.8%, solid-liquid separation, and separating obtained liquid is high potassium bittern one; By high potassium bittern one evaporation concentration, be evaporated to liquid phase containing potassium 2.0-2.5%(mass percent again), carry out solid-liquid separation, gained solid is potassium mixed salt, separating obtained liquid is for analysing potassium bittern.
The method of potassium ores is produced in above-mentioned utilization containing the magnesium sulfate bittern of nitrate, be characterised in that: described in analyse potassium bittern for analysing potassium mother liquor, or make as follows analyse potassium bittern: get magnesium sulfate intercrystalline bittern spontaneous evaporation that six-membered system contains nitrate to liquid phase containing potassium 3.9%(mass ratio), then carry out solid-liquid separation, separating obtained liquid phase is high potassium bittern two, high potassium bittern two is continued to spontaneous evaporation and analyse potassium, be evaporated to liquid phase containing potassium 2.3%, again carry out solid-liquid separation, separating obtained liquid phase is for analysing potassium bittern.
The magnesium sulfate intercrystalline bittern that utilization contains nitrate is produced the method for saltpetre, comprises the following steps:
1. the method for producing potassium ores by utilization claimed in claim 1 containing the magnesium sulfate bittern of nitrate is prepared potassium mixed salt;
2. potassium mixed salt purification removal of impurities: above-mentioned potassium mixed salt is carried out to ball milling in solid-liquid mass ratio 1:2 ratio batching, and the liquid of solid-liquid batching use is flotation mother liquor, and the slip after ball milling first sieves, and screen overflow major ingredient is epsom salt; Screen underflow is carried out to flotation, and flotation reagent is selected hydrochloric acid stearylamine, the foam on liquid level is scraped with scraping plate of flotation machine, obtains flotation froth and flotation mother liquor;
3. saltpetre is refining: in the flotation froth obtaining to the removal of impurities of above-mentioned potassium mixed salt, add cold analysis mother liquor thermosol, thermosol temperature is controlled at 50 ℃～115 ℃, and the add-on of cold analysis mother liquor is by the K in hot solution
+content control, controls K in hot solution
+content is in 18%～28%(mass percent), then insulation separates, and separate solid is called high temp. salt, and separating liquid is called hot solution; The cooling rear solid-liquid separation of hot solution obtains containing saltpetre 95%(mass percent) above Temperature and cold analysis mother liquor;
By Temperature: crystalline mother solution (mass ratio)=1:0.7～1 adds crystalline mother solution in above-mentioned Temperature, normal temperature washing separated after 30 minutes, and separating and obtaining solid is smart potassium, and separating and obtaining liquid is thick potassium washings; In smart potassium, add fresh water by the mass ratio of 1:0.4～0.43, thermosol at 100 ℃～110 ℃, after the pressure of thermosol liquid is cooling, separating out solid is the wet product of saltpetre, liquid is crystalline mother solution.
above-mentionedthe magnesium sulfate intercrystalline bittern that utilization contains nitrate is produced the method for saltpetre: carry out drip washing to high temp. salt surface sprinkling fresh water, then use fresh water agitator treating at 50 ℃～80 ℃, the add-on of fresh water is to wash the K in rear high temp. salt
+content is less than 1.0%(mass percent) control, then carry out drip washing separation, the separating obtained liquid of drip washing is leacheate, drip washing is salt lake intercrystalline bittern pulp washing for separating obtained solid, the solid, liquid of sizing mixing again separates, and the separating obtained solid major ingredient of the solid, liquid of sizing mixing is sodium-chlor and sodium sulfate; The liquid phase that the solid, liquid of sizing mixing separates is washings, mixes rear evaporation with leacheate, superfluous cold analysis liquid, thick potassium washings, and blending proportion is to mix K in rear mixed solution
+: NO
3 -ratio (mass ratio) control, control K in mixed solution
+: NO
3 -=1:1.6～2.4, are evaporated to liquid phase containing K by mixed solution
+be 18%～28%(mass percent), then the hot solution of being returned in saltpetre refining step is incubated separation.
above-mentionedthe magnesium sulfate intercrystalline bittern that utilization contains nitrate is produced the method for saltpetre, by wet described saltpetre product drying.
Beneficial effect 1. utilizes the magnesium sulfate intercrystalline bittern that contains nitrate to produce the method for potassium mixed salt compared with the saltpetre of nitrate type bittern production in the past Technology, does not need to add any demagging agent.
2. halogen technology is converted in ingenious employing, and the bittern composition that makes to convert after halogen enters the saturated phase region of epsom salt, has avoided potassium magnesium sulfate double salt phase region; Due to common-ion effcet effect, moment is separated out part epsom salt and sodium-chlor, after epsom salt and sodium-chlor have been separated out in continuation spontaneous evaporation, bittern composition enters the saturated phase region of potassium, obtain potassium saturated bittern, reach the object of removing magnesium sulfate, avoid again containing separating out in advance of potassium double salt, greatly improved the quality of yield and the potassium mixed salt of potassium.The mode that the magnesium sulfate intercrystalline bittern that six-membered system contains nitrate is converted halogen by employing has been removed magnesium sulfate, has avoided adopting high temperature evaporation in the past or has added the mode that demagging agent is removed magnesium sulfate.
3.
the major advantage of this method is to adopt salt pan spontaneous evaporation, makes full use of local unique physical environment and weather condition, has changed and has adopted forced evaporation to produce the method for intermediate raw material in the past;it is containing the high potassium mixed salt solid mineral of saltpetre quality that this technique can adopt salt pan spontaneous evaporation classification to shine the intermediates that make, the intermediates that the Technology in past obtains after evaporating by salt pan are potassium saturated bitterns, potassium saturated bittern is produced saltpetre by workshop forced evaporation, and original process energy consumption is high, equipment corrosion is serious.
Utilize magnesium sulfate intercrystalline bittern that six-membered system contains nitrate to produce the method for saltpetre, adopt purification by floatation potassium mixed salt, technical process is shortened, facility investment reduces, simple to operate: hydrochloric acid stearylamine is attached to potassium nitrate crystals surface, only increase the hydrophobicity on potassium nitrate crystals surface and potassium nitrate crystals is swum on liquid level, other salt sinks to flotation cell bottom, by scraping plate of flotation machine, foam is scraped, realized separating of saltpetre and other salt; Flotation froth is mainly the saltpetre that contains a small amount of sodium-chlor, magnesium sulfate, and wherein potassium nitrate content is 70%～80%,
Adopt the present invention not only can produce qualified technical grade saltpetre, but also can by-product magnesium sulfate heptahydrate, saltcake, sodium-chlor etc.
The present invention is better than original nitrate type bittern and produces saltpetre technique, it has, and demagging agent, employing flotation technology simply, are not added in technical process, energy consumption is low, facility investment is low, equipment corrosion is light, quality product is high, low cost and other advantages, are suitable for the magnesium sulfate Brine resources that the brave Bu Lake of scale development crow salt lake six-membered system contains nitrate.
The potassium bittern of analysing of the present invention refers to and analyses K after potassium
+the bittern that content (mass ratio) is 2.0%～2.5%, Mg content (mass ratio) is 5.0%～7.5%.
Of the present invention
analyse potassium mother liquor:sodium-chlor, magnesium sulfate, saltpetre and carnallitite be saturated bittern altogether;
Of the present invention
high-sulfur bittern:sodium-chlor, saltcake and potassium magnesium sulfate double salt is saturated bittern altogether;
Of the present invention
high potassium bittern one: sodium-chlor, magnesium sulfate and saltpetre is saturated bittern altogether;
Of the present invention
high potassium bittern two: sodium-chlor, potassium magnesium sulfate double salt and saltpetre is saturated bittern altogether.
Accompanying drawing explanation
Fig. 1 utilizes the schema of producing potassium ores and production saltpetre containing the magnesium sulfate bittern of nitrate.
Embodiment
following embodimentsalt lake used intercrystalline bittern is taken from crow honor Bu Lake salt lake, Turfan Prefecture intercrystalline bittern, and this brine composition content is in Table 1(because the difference in season is different with the place of adopting halogen, and composition is fluctuation slightly).
Table 1: Turfan Prefecture crow honor Bu Lake salt lake intercrystalline bittern composition data (unit: %)
| Title | K + | Mg 2+ | Na + | Cl - | SO 4 2- | NO 3 - | H 2O |
| Intercrystalline bittern | 0.15～0.25 | 0.25～0.4 | 9.9～10.4 | 14.8～15.2 | 1.5～2.5 | 0.5～0.7 | 72.9～70.6 |
embodiment mono-:
1. potassium mixed salt is produced:
Single stage desalting: get black honor Bu Lake salt lake intercrystalline bittern 1000Kg, being placed on multiple bores is 50cm, the degree of depth is in the plastic tub of 20cm, concentrated in laboratory spontaneous evaporation, is evaporated to liquid phase containing potassium 1.27%, separate with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid phase referred to herein as sodium-chlor, sodium chloride content reaches more than 95%, meets Industrial Salt service requirements completely, separate liquid phase referred to herein as sodium sulfate saturated bittern, it proceeds spontaneous evaporation concentrating and desalinating.
Secondary desalination: it is 50cm that sodium sulfate saturated bittern is placed in to multiple bores, the degree of depth is in the plastic tub of 20cm, concentrated in spontaneous evaporation, be evaporated to liquid phase containing potassium 2.05%, separate with the link-suspended basket centrifuge that rotary drum is 40cm, separation solid phase is referred to herein as abraum salt, it is the mixture of sodium sulfate and sodium-chlor, separating liquid phase is the bittern that containing sulfate radicals is higher, and referred to herein as high-sulfur bittern, it uses as converting halogen raw brine.
Convert halogen: by high-sulfur bittern: the mass ratio of analysing potassium bittern is 1:0.8, mix and mix, moment is separated out a small amount of sodium-chlor and magnesium sulfate simultaneously, mix liquid referred to herein as converting saltwater brine, then converting saltwater brine, to be placed in multiple bores be 50cm, the degree of depth is in the plastic tub of 20cm, concentrated in laboratory spontaneous evaporation, be evaporated to liquid phase containing potassium 3.25%, separate with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid phase referred to herein as epsom salt, it is mainly the mixture of magnesium sulfate heptahydrate and sodium-chlor, separating liquid phase is potassium saturated bittern, it carries out spontaneous evaporation and analyses potassium.
analyse potassium:it is 50cm that potassium saturated bittern is placed in to multiple bores, the degree of depth is that in the plastic tub of 20cm, in laboratory, potassium is analysed in spontaneous evaporation, along with the carrying out of evaporation, potassium mixed salt is constantly separated out, liquid phase potassium content reduces gradually, is evaporated to liquid phase containing potassium 2.24%, separates with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid phase referred to herein as potassium mixed salt, it is the mixture of potassium nitrate that contains a small amount of magnesium sulfate heptahydrate, sodium-chlor, separates liquid phase for analysing potassium mother liquor, and it recycles.
convert halogen standby with analysing potassium making from brine:get brave Bu Lake salt lake salt pan, the lake region spontaneous evaporation of crow to the bittern of liquid phase containing potassium 2%, being contained in multiple bores is 47cm*35cm, the degree of depth is in the plastic tub of 40cm, in family expenses Haier refrigerator-freezer, freezing 48h below-5 ℃, then separate with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid phase referred to herein as ice nitre, it is mainly the sal glauberi that contains a small amount of sodium-chlor, separate liquid phase for freezing bittern after nitre, to freeze after nitre bittern, to be placed in multiple bores be 50cm, the degree of depth is in the plastic tub of 20cm, concentrated in laboratory spontaneous evaporation, be evaporated to liquid phase containing potassium 3.9%, Mg
2+when content (mass percent) is 4.45%, separate with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid phase and be mainly sodium-chlor, separating liquid phase is high potassium bittern one, again high potassium bittern one being placed in to multiple bores is 50cm, the degree of depth is in the plastic tub of 20cm, concentrated in laboratory spontaneous evaporation, be evaporated to liquid phase containing potassium 2.3%, separate with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid phase at this be also referred to as-potassium mixed salt, it is the mixture of potassium nitrate that contains a small amount of magnesium sulfate heptahydrate, sodium-chlor, and it is the raw material of producing saltpetre, separate liquid phase for analysing potassium mother liquor, it is as the above-mentioned halogen process raw brine of converting.
In this process, main material data and content thereof show in table 2.
Table 2: potassium mixed salt is produced the each material data of process stage and content thereof
2. potassium mixed salt removal of impurities:
ball milling:get the potassium mixed salt 0.6Kg that 1. operation analyses potassium process output, dividing equally is two parts, in potassium mixed salt: the ratio batching of flotation mother liquor mass ratio 1:2, use at twice QM (0～5L) laboratory tumbling ball mill to carry out ball milling, Ball-milling Time is 20min, originally mother liquor fresh water, after recycle;
screening:slip after ball mill ore grinding sieves with 60 mesh standard sieves, and on-the-sieve material is rinsed with a small amount of flotation mother liquor, and screen overflow is referred to herein as epsom salt, and it is mainly the magnesium sulfate heptahydrate that contains a small amount of sodium-chlor, and minus mesh slurry is as the raw material of floatation process;
flotation:minus mesh slurry is inserted in X-d III-3L unit flotation cell, supplement flotation mother liquor simultaneously, control liquid level apart from discharge port 1cm place, after add the 2%(mass percent preparing) flotation reagent 5ml, mix 2min, regulate flotation machine engine speed to 1000rpm, air-blowing amount 0.12L/min, froth paddle rotating speed 30rpm, flotation 4min, select solid referred to herein as flotation froth, it is after XS200-2.8L experiment is with centrifuge dewatering, be mainly and contain a small amount of sodium-chlor, the saltpetre of magnesium sulfate, potassium nitrate content is 76.13%, it is as saltpetre refining step raw material 3., after separating, liquid phase is flotation mother liquor, it recycles,
flotation salt processing:flotation residue slip separates with XS200-2.8L whizzer, separating liquid is flotation mother liquor, it recycles, separate solid is referred to herein as flotation salt, main component is sodium-chlor, be placed in 1000ml beaker, size mixing with salt lake intercrystalline bittern, intercrystalline bittern add-on is by flotation salt: intercrystalline bittern mass ratio 0.88:1 adds, with JJ-1 type experiment electric mixer agitator treating 15min, separate with XS200-2.8L experiment whizzer again, separate solid is referred to herein as sodium-chlor, its content reaches more than 95%, meet Industrial Salt service requirements completely, separate liquid phase referred to herein as returning solution one, its component concentration reaches the 1. sodium sulfate saturated bittern component concentration of single stage desalting process of operation, it is directly returned to secondary demineralising process recycles.
The potassium mixed salt 10.51Kg that 1. operation is analysed to potassium process output by above-mentioned steps gradation, circular treatment after, in process, each main material integrated data and content thereof show in table 3.
Table 3: the each material data of potassium mixed salt removal of impurities process stage and content thereof
Table 3: the each material data of potassium mixed salt removal of impurities process stage and content thereof
3. saltpetre is refining:
thermosol removal of impurities:get the operation flotation froth 0.6Kg that 2. floatation process obtains, be placed in the beaker of 1000ml, add cold analysis mother liquor simultaneously, originally mother liquor fresh water, stir with JJ-1 type experiment electric mixer, at the heating by electric cooker thermosol of 1000W, thermosol temperature is controlled at 105 ℃, and the add-on of cold analysis mother liquor is by the K in hot solution
+content control, controls K in hot solution
+content is 23%, be heated to after 105 ℃, insulated and stirred 5min, then use SHZ-D III water circulating type vacuum pump suction filtration, the boiling preheating in hot water by 2500ml filter flask and ￠ 210 Büchner funnels before suction filtration, in filter flask, add a small amount of fresh water simultaneously, fresh water add-on adds by 12% of hot solution quality, after suction filtration separates, liquid is referred to herein as high-temperature liquid, high-temperature liquid is for crystallisation by cooling, separate solid is high temp. salt, for high temp. salt drip washing, (thermosol temperature is controlled at 50 ℃～115 ℃ according to the difference of lectotype selection in washing, select different control temperature, temperature is higher, yield is higher, 115 ℃ approach the boiling point of hot solution).
high temp. salt drip washing, washing: a small amount of fresh water of high temp. salt surface sprinkling after separating to thermosol removal of impurities process in Büchner funnel, use SHZ-D III water circulating type vacuum pump suction filtration simultaneously, fresh water sprinkling amount is as the criterion for one time with high temp. salt surface uniform spray, parting liquid is leacheate, it inserts the storage of 2000ml beaker, to mother liquid evaporation process, separate solid is drip washing solid, inserted 500ml beaker, add appropriate fresh water, with the stirring of JJ-1 type experiment electric mixer, at the heating by electric cooker of 1000W, wash temperature is 80 ℃, and the add-on of fresh water is to wash the K in rear high temp. salt
+content is less than 1% control, SHZ-D III water circulating type vacuum pump suction filtration for washing slip, separating liquid is referred to as high temp. salt washings at this, it is together stored with leacheate above, to mother liquid evaporation process, separate solid is referred to as high temp. salt at this, it is mainly sodium-chlor and a small amount of sodium sulfate, inserted 500ml beaker, size mixing with salt lake intercrystalline bittern, intercrystalline bittern add-on is by high temp. salt: intercrystalline bittern mass ratio 0.88:1 adds, with JJ-1 type experiment electric mixer agitator treating 15min, separate with XS200-2.8L experiment whizzer again, separate solid is referred to herein as sodium-chlor, its content reaches more than 95%, meet Industrial Salt service requirements completely, separate liquid phase referred to herein as returning solution two, its component concentration reaches the 1. sodium sulfate saturated bittern component concentration of single stage desalting process of operation substantially, it is directly returned to secondary demineralising process recycles.
crystallisation by cooling:high-temperature liquid after thermosol removal of impurities process suction filtration is separated is inserted in 2000ml beaker, use cold water indirect heat exchange, force cooling, stir with JJ-1 type experiment electric mixer simultaneously, until high-temperature liquid temperature is cooled to 25 ℃, then separate with XS200-2.8L experiment whizzer, separate solid is referred to herein as Temperature, its purity reaches more than 95%, Temperature is carried out to thick potassium washing, and separating liquid is cold analysis mother liquor, the most of molten removal of impurities process of reducing phlegm and internal heat that circulates of cold analysis mother liquor, residue cold analysis mother liquor and above leacheate are together stored, to mother liquid evaporation process.
thick potassium washing:the Temperature that crystallisation by cooling process is obtained is inserted 1000ml beaker, add a small amount of thick potassium washings of fresh water or crystalline mother solution and last time simultaneously, (use at first fresh water, the crystalline mother solution by postorder operation has been opened in circulation later), additional proportion is Temperature: the mass ratio=1:0.9 of mother liquor, use electric mixer agitator treating 30 minutes in normal temperature with the experiment of JJ-1 type, then separate with XS200-2.8L experiment whizzer, separate solid is referred to herein as smart potassium, its duplicate removal crystallization, separating liquid is thick potassium washings, thick potassium washings part is back to thick potassium washing next time, remaining thick potassium washings together stores with leacheate above, to mother liquid evaporation process.
recrystallization:thick potassium is washed to the smart potassium obtaining and insert 1000ml beaker, add fresh water by the mass ratio of 1:0.4, stir with JJ-1 type experiment electric mixer, at the heating by electric cooker thermosol of 1000W, thermosol temperature is controlled at 110 ℃, after dissolving completely, use cold water indirect heat exchange, force cooling, stir with JJ-1 type experiment electric mixer simultaneously, until high-temperature liquid temperature is cooled to 25 ℃, then separate with XS200-2.8L experiment whizzer, separate solid is referred to herein as wet saltpetre, it is to drying process, separating liquid is crystalline mother solution, it turns back to thick potassium washing next time completely.
dry: the wet saltpetre that recrystallization is obtained is laid in the enamel pallet of 300mm*200mm, inserts in 101-1 type Constant Temp. Oven, and dry 60min at 105 ℃, dry rear material is the technical grade premium grads saltpetre product that purity is greater than 99.7%.
mother liquid evaporation:mixed leacheate, high temp. salt washings, superfluous cold analysis mother liquor, superfluous thick potassium washings are inserted to 2000ml beaker, use JJ-1 type experiment electric mixer to stir, in the heating by electric cooker evaporation of 1000W, be evaporated to mixed solution liquid phase containing K
+23%, return it to the separating step of this operation thermosol removal of impurities process, repeat above process.
By operation, 2. the flotation froth 4.91Kg of floatation process output is by after above-mentioned steps gradation, circular treatment, and in process, each main material integrated data and content thereof show in table 4.
Table 4: each material data of saltpetre treating process stage and content thereof
Table 4: each material data of saltpetre treating process stage and content thereof
By this technique, utilizing the brave Bu Lake of crow salt lake intercrystalline bittern to produce saltpetre executes feasible, can arrive 63.6% by this technique potassium ion yield after laboratory experiment, nitrate ion yield can reach 40.35%, and it is 303.31 tons that ton saltpetre consumes the brave Bu Lake of crow salt lake intercrystalline bittern amount.
This technological process output saltpetre is pressed GB 1918-2011 industrial potassium nitrate standards and is carried out, and indices mensuration situation is in table 5.
Table 5: this technological process output saltpetre indices is measured situation
+ [0039]the title of flotation reagent: hydrochloric acid stearylamine
The preparation of flotation reagent: the industrial concentrated hydrochloric acid more than 35% is according to 1:1.2(mass percent by stearylamine and concentration) ratio carry out hybrid reaction, after stearylamine is dissolved in concentrated hydrochloric acid completely, then add be not less than the hot water of 60 ℃ the content of hydrochloric acid stearylamine be diluted to 2%(mass percent).
The using method of flotation reagent: potassium mixed salt slip is imported in flotation machine, add by following dosage the flotation reagent preparing simultaneously, stir by flotation machine main shaft, make flotation reagent intersperse among uniformly potassium mixed salt slip the inside, in slip, do not stop to blast air with flotation machine air pump simultaneously, the flotation reagent surface tension that is attached with potassium nitrate crystals increases, producing bubbles moves upward, potassium nitrate crystals is swum on potassium mixed salt slip table liquid level, other salt sinks to flotation cell bottom, by scraping plate of flotation machine, the potassium nitrate crystals swimming on potassium mixed salt slip table liquid level is scraped, realize separating of saltpetre and other salt.
The consumption of flotation reagent: the consumption of stearylamine is controlled according to the height of potassium content in potassium mixed salt, and potassium mixed salt potassium content is higher, the quantity that unit potassium mixed salt consumes stearylamine is with regard to corresponding increase.According to the potassium mixed salt potassium content of this technology method output, 12%～18%, in this content interval situation, the amount that potassium mixed salt per ton consumes stearylamine can be controlled in 150g～200g.
[0039] willpotassium mixed salt slip
putenter X-d III-3L unit flotation cell
in, add in proportion the flotation reagent preparing simultaneously,
pass throughflotation machine main shaft stirs, and makes flotation reagent intersperse among uniformly potassium mixed salt slip the inside,
andbe attached to potassium nitrate crystals surface, increased the hydrophobicity on potassium nitrate crystals surface,
simultaneouslyflotation machine air pump does not stop to blast air in slip,
the flotation reagent surface tension that is attached with potassium nitrate crystals increases, and producing bubbles moves upward,potassium nitrate crystals is swum in
potassium mixed salt slip tableon liquid level, other salt sinks to flotation cell bottom, will swim in by scraping plate of flotation machine
potassium mixed salt slip tablepotassium nitrate crystals on liquid level scrapes, and realized separating of saltpetre and other salt.
Adopt concentrated hydrochloric acid to dissolve stearylamine faster than adopting diluted hydrochloric acid dissolution stearylamine dissolution rate, reaction thoroughly.
In the above-described embodiments, the washings separating in saltpetre purification step and leacheate, superfluous cold analysis liquid, thick potassium washings are mixed rear evaporation, and blending proportion is to mix K in rear mixed solution
+: NO
3 -ratio control, control K in mixed solution
+: NO
3 -=1:1.6～2.4, are evaporated to liquid phase containing K by mixed solution
+18%～28%
(in this principal security evaporative process liquid phase potassium ion in state of saturation, liquid phasek
+ lower than 18%, it will exist with other salt form, reduce potassium ion yield; Liquid phasek
+ higher than 28%, potassium ion will be separated out with saltpetre form, increase potassium, nitrate radical loss; Meanwhile, according to the height of slip solid content, the liquid phase potassium ion in evaporative process is regulated and controled, solid content, higher than 60%, is suitably turned down the concentration of evaporation liquid phase potassium ion, and solid content, lower than 30%, can suitably be heightened the concentration of evaporation liquid phase potassium ion), return it to this operation hot solution and be incubated separation, repeat above process.
describedin the above Temperature of purity 95%, add crystalline mother solution, additional proportion is Temperature: mass ratio=1:0.7～1 of crystalline mother solution
(wash concentration is controlled at below 60%, can guarantee that material fully stirs with slurry state, and can guarantee the washing effect of impurities ion in Temperature), separating after 30 minutes in normal temperature washing, separate solid is smart potassium, and smart potassium is carried out to recrystallization, and separating liquid is thick potassium washings, and it is to evaporation; In smart potassium, add fresh water by the mass ratio of 1:0.4～0.43, at 100 ℃～110 ℃
(solubleness of saltpetre increases along with the rising of temperature, and under normal pressure, the boiling point of saltpetre saturated solution can also reach 113 ℃, lower in this solvent temperature, and amount of water certainly will increase, and yield certainly will reduce; Simultaneously for guaranteeing recrystallization product quality, in actual mechanical process, according to smart potassium impurity ion content, capable of regulating recrystallization process amount of water, make it thermosol under corresponding temperature of saturation, be that smart potassium impurity ion content is relatively higher, we can increase recrystallization amount of water, and thermosol temperature can correspondingly decline like this; Essence potassium impurity ion content is relatively on the low side, and we can reduce recrystallization amount of water, the corresponding rising of thermosol temperature like this)lower thermosol, thermosol liquid is forced after cooling (using tap water circulating cooling), and separating out solid is the wet product of saltpetre, after being dried, is the technical grade premium grads saltpetre that purity is greater than 99.7%, and liquid is crystalline mother solution, and it removes to wash Temperature.
In above-described embodiment,
in the secondary desalination step that potassium mixed salt is produced,sodium sulfate saturated bittern is evaporated to liquid phase containing potassium (mass ratio)
requirement that 2.0%～3.2% all can meeting tier 2 desalination, convert halogen, analyse potassium process.liquid phase containing potassium (mass ratio) higher than
3.2% time, potassium ion will be separated out in advance, in abraum salt, will contain sylvite, and the follow-up potassium process of analysing separates out that potassium mixed salt quantity reduces to some extent, potassium yield reduces relatively;liquid phase containing potassium (mass ratio) lower than
2.0% time, sodium sulfate is separated out not exclusively, causes the quality of potassium mixed salt to reduce; Control to this index 2.0%～3.2%, follow-up analyse potassium process separate out potassium mixed salt quantity at most, potassium yield is the highest.
In above-described embodiment,
what potassium mixed salt was produced converts in halogen step:by high-sulfur bittern: the mass ratio of analysing potassium bittern is 1:0.8
～1.6 control index all can meet the requirement of converting halogen, analysing potassium process, but this ratio higher than1:0.8 time
, the follow-up potassium process of analysing separates out that potassium mixed salt quantity reduces to some extent, potassium yield reduces relatively; Control to after this index condition, follow-up analyse potassium process separate out potassium mixed salt quantity at most, potassium yield is the highest.
In above-described embodiment,
screening step in the removal of impurities of potassium mixed salt:slip after ball mill ore grinding
with60 order-100 orders
order is counted standard sieve screening arbitrarily, all can realize the object of screening, selects different screening order numbers, and epsom salt screening effect is by difference.
In above-described embodiment,
in high temp. salt drip washing in saltpetre is refining, washing step,wash temperature general control is at 50 ℃～80 ℃,
the potassium ion containing in high temp. salt after drip washing mainly exists with kainite form, selects this temperature range, and object is to make potassium ion and nitrate ion fully to transform, make potassium ion enter liquid phase, be convenient to reclaim, the too low conversion that is unfavorable for potassium ion of temperature, the too high heat energy consumption of temperature is high.
embodiment bis-:just be with the difference of embodiment mono-, in embodiment mono-, operation is converted halogen process in the middle of 1., high-sulfur bittern: the mass ratio of analysing potassium bittern is 1:0.8, in the present embodiment, this ratio is in high-sulfur bittern: the situation after the ratio that the mass ratio of analysing potassium bittern is 1:1.6 is carried out is as following:
?convert halogen: by high-sulfur bittern: the mass ratio of analysing potassium bittern is 1:1.6, mix and mix, moment is separated out a small amount of sodium-chlor and magnesium sulfate simultaneously, mix liquid referred to herein as converting saltwater brine, then converting saltwater brine, to be placed in multiple bores be 50cm, the degree of depth is in the plastic tub of 20cm, concentrated in laboratory spontaneous evaporation, be evaporated to liquid phase containing potassium 3.36%, separate with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid phase referred to herein as epsom salt, it is mainly the mixture of magnesium sulfate heptahydrate and sodium-chlor, separating liquid phase is potassium saturated bittern, adopt spontaneous evaporation mode to evaporate to potassium saturated bittern and analyse potassium.
Convert after halogen and high-sulfur bittern by this ratio: the mass ratio of analysing potassium bittern is that 1:0.8 converts halogen and high-sulfur bittern: the mass ratio of analysing potassium bittern is that halogen is converted in interval, 1:0.8～1.6, essential distinction is, convert saltwater brine and in spontaneous evaporation process, separate out the quantity of epsom salt, the corresponding minimizing of evaporation duration, shortening, the corresponding minimizing of potassium mixed salt quantity that potassium saturated bittern is analysed output in potassium process in later stage spontaneous evaporation.
After implementing by the present embodiment, potassium mixed salt is produced the each material data of process stage and content thereof in table 6.
Table 6: potassium mixed salt is produced the each material data of process stage and content thereof
embodiment tri-:just be with the difference of embodiment mono-, in embodiment mono-, operation is converted halogen in the middle of 1. with analysing potassium mother liquor preparation process bittern used containing potassium 2%, in the present embodiment, convert halogen with analyse potassium mother liquor preparation process bittern used containing potassium be situation after 2.38% as following:
convert halogen standby with analysing potassium making from brine:get salt pan, the lake region spontaneous evaporation of black honor Bu Lake salt lake to the bittern of liquid phase containing potassium 2.38%, being contained in multiple bores is 47cm*35cm, the degree of depth is in the plastic tub of 40cm, in family expenses Haier refrigerator-freezer, at-8 ℃ of freezing 48h, then separate with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid phase referred to herein as ice nitre, it is mainly the sal glauberi that contains a small amount of sodium-chlor, separate liquid phase for freezing bittern after nitre, to freeze after nitre bittern, to be placed in multiple bores be 50cm, the degree of depth is in the plastic tub of 20cm, concentrated in laboratory spontaneous evaporation, be evaporated to liquid phase containing potassium 3.66%, Mg
2+when content (mass percent) is 4.53%, separate with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid phase and be mainly sodium-chlor, separating liquid phase is high potassium bittern one, again high potassium bittern one being placed in to multiple bores is 50cm, the degree of depth is in the plastic tub of 20cm, concentrated in laboratory spontaneous evaporation, is evaporated to liquid phase containing potassium 2.17%, Mg
2+content (mass percent) is 7.22%, separates with the link-suspended basket centrifuge that rotary drum is 40cm, separates solid phase at this be also referred to as-potassium mixed salt, and it is the mixture of potassium nitrate that contains a small amount of magnesium sulfate heptahydrate, sodium-chlor, and it is the raw material of producing saltpetre, separate liquid phase for analysing potassium mother liquor, it is as the above-mentioned halogen process raw brine of converting.Making from brine by this potassium content is standby analyses potassium mother liquor and potassium content and produces at the bittern in 2% and 2.% to 2.4% interval the quantity that the essential distinction of analysing potassium mother liquor separates out ice nitre in being just refrigerating process and reduce to some extent.
Table 7: analyse potassium bittern preparation process bittern content
embodiment tetra-:just be with the difference of embodiment mono-, in embodiment mono-, operation is converted halogen in the middle of 1. potassium making from brine is standby also can be realized by the following method with analysing:
Get salt pan, the lake region spontaneous evaporation of black honor Bu Lake salt lake and contain more than 2% bittern of potassium to liquid phase, being placed on multiple bores is 50cm, in the plastic tub that the degree of depth is 20cm, concentrated in laboratory spontaneous evaporation, is evaporated to liquid phase containing potassium to 3.96%, Mg
2+when content (mass percent) is 5.33%, separate with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid is referred to herein as abraum salt, it is mainly with potassium, magnesium, the double salt that sulfate radical double salt form exists and a large amount of sodium-chlor, discarded, separating liquid phase is potassium saturated bittern, it is 50cm that potassium saturated bittern is placed in to multiple bores, the degree of depth is in the plastic tub of 20cm, in laboratory, potassium is analysed in spontaneous evaporation, be evaporated to liquid phase containing potassium 2.3%, separate with the link-suspended basket centrifuge that rotary drum is 40cm, separate solid phase and be also referred to as assorted potassium mixed salt at this, it is for containing in a large number with potassium, magnesium, several double salt and sodium-chlor that sulfate radical double salt form exists, the mixture of saltpetre, it is continued to employ, separate liquid phase for analysing potassium bittern, it also can be used as the above-mentioned halogen process raw brine of converting.After the assorted potassium mixed salt of separating out, can soak and dissolve with former halogen, to reclaim the useful components such as the potassium of mixing in potassium mixed salt, the bittern after immersion again deduplication example one such as evaporates at the sequence of operations.
In process, high potassium bittern two content of output show in table 8.
Table 8: high potassium bittern two content
embodiment five:the basic skills of the present embodiment and step are with embodiment mono-, embodiment bis-, embodiment tri-, embodiment tetra-differences:
The process of producing of potassium mixed salt realizes by salt pan spontaneous evaporation.
Potassium mixed salt is produced:
Single stage desalting: get approximately 5000 tons of black honor Bu Lake salt lake intercrystalline bitterns, be placed on the pond spontaneous evaporation of one-level sodium concentrated, be evaporated to liquid phase containing potassium 1.33%, liquid phase is referred to herein as sodium sulfate saturated bittern, and it imports secondary sodium pond with pump and carries out spontaneous evaporation concentrating and desalinating, solid phase is referred to herein as sodium-chlor, its content is 96.31%, meets Industrial Salt service requirements completely, and it goes out intergranular by artificial ditching drop and presss from both sides the bittern of depositing, solid phase Ji Dui stores, and drop goes out bittern and imports in the lump secondary sodium pond.
Secondary desalination: the sodium sulfate saturated bittern that one-level sodium pond is imported, be placed in the pond spontaneous evaporation of secondary sodium concentrated, be evaporated to liquid phase containing potassium 2.12%, liquid phase is the bittern that containing sulfate radicals is higher, referred to herein as high-sulfur bittern, it imports bittern-mixing pool with pump and uses as converting halogen raw brine, solid phase is referred to herein as abraum salt, and it is the mixture of sodium sulfate and sodium-chlor, and it goes out intergranular by artificial ditching drop and presss from both sides the bittern of depositing, solid phase Ji Dui stores, and drop goes out bittern and imports in the lump bittern-mixing pool.
Convert halogen: the high-sulfur bittern that secondary sodium pond is imported, be placed in bittern-mixing pool, simultaneously in high-sulfur bittern: the ratio importing that the mass ratio of analysing potassium bittern is 1:0.9 is analysed potassium mother liquor and mixed, mix liquid referred to herein as converting saltwater brine, it is concentrated in bittern-mixing pool spontaneous evaporation, be evaporated to liquid phase containing potassium 3.4%, liquid phase is referred to herein as potassium saturated bittern, it imports the spontaneous evaporation of sylvite pond with pump and analyses potassium, solid phase is referred to herein as epsom salt, it is mainly the mixture of magnesium sulfate heptahydrate and sodium-chlor, it goes out intergranular by artificial ditching drop and presss from both sides the bittern of depositing, solid phase Ji Dui stores, drop goes out bittern and imports in the lump sylvite pond.
Convert halogen and use the source of analysing potassium bittern: be stored in the intercrystalline bittern in salt pan, black honor Bu Lake salt lake early stage, by the method for embodiment bis-, the bittern making in salt pan.
Analyse potassium: the potassium saturated bittern that bittern-mixing pool is imported, is placed in the spontaneous evaporation of sylvite pond and analyses potassium, along with the carrying out of evaporation, potassium mixed salt is constantly separated out, liquid phase potassium content reduces gradually, is evaporated to liquid phase containing potassium 2.5%, and liquid phase is for analysing potassium mother liquor, it recycles, solid phase is referred to herein as-potassium mixed salt, and it is the mixture of potassium nitrate that contains a small amount of magnesium sulfate heptahydrate, sodium-chlor, and it goes out intergranular by artificial ditching drop and presss from both sides the bittern of depositing, solid phase Ji Dui stores, as the raw material of producing saltpetre.
Produced process and made the potassium mixed salt of 48 tons of left and right by above-mentioned potassium mixed salt, its quality is better than the quality of the potassium mixed salt that embodiment mono-operating process obtains, and its data are in table 9.
Table 9: potassium mixed salt is produced process and made potassium mixed salt data
Can be according to salt pan situation, to the evaporation described in above-described embodiment, convert halogen, analyse potassium place and change, described intercrystalline bittern passes through evaporation concentration in sodium salt field; Described high potassium bittern imports equalizing tank and is blended into analyses potassium bittern, and precipitated sodium chloride and magnesium sulfate, must convert saltwater brine; The described saltwater brine of converting is imported into potassium mixed salt pond evaporation and analyses potassium.
above-mentionedthe magnesium sulfate intercrystalline bittern that utilization contains nitrate is produced the method for saltpetre, and the wet saltpetre that recrystallization is obtained is laid in enamel pallet, inserts in Constant Temp. Oven, and at 105 ℃, dry 60min, can obtain technical grade saltpetre product.
The described potassium bittern of analysing, can make as follows respectively at the beginning of the cycle: it is concentrated containing the more than 2% bittern spontaneous evaporation of potassium to liquid phase to get the magnesium sulfate intercrystalline bittern spontaneous evaporation that six-membered system contains nitrate, be evaporated to liquid phase containing potassium to 3.9%, then carry out solid-liquid separation, separate solid is referred to herein as abraum salt, it is mainly the double salt and a large amount of sodium-chlor that exist with potassium, magnesium, sulfate radical double salt form, is discarded; Separating liquid phase is potassium saturated bittern, potassium saturated bittern is continued to spontaneous evaporation and analyse potassium, be evaporated to liquid phase containing potassium 2.3%, again carry out solid-liquid separation, separate solid phase referred to herein as assorted potassium mixed salt, it is the mixture that contains several double salt of existing with potassium, magnesium, sulfate radical double salt form in a large number and sodium-chlor, saltpetre, and it soaks dissolving with salt lake intercrystalline bittern, the useful components such as the potassium in the assorted potassium mixed salt of recovery, it is concentrated that the bittern after immersion repeats spontaneous evaporation; Separate liquid phase for analysing potassium bittern, it also can be used as the above-mentioned halogen process raw brine of converting.
Claims (7)
1. utilize the method for producing potassium ores containing the magnesium sulfate bittern of nitrate, comprise the following steps:
1. the magnesium sulfate intercrystalline bittern that six-membered system is contained to nitrate, by evaporation concentration, is separated out abraum salt, K in bittern
+when content (mass ratio) is 2.0%～3.2%, separate abraum salt, obtain high-sulfur bittern;
2. convert halogen: by high-sulfur bittern: analyse that potassium bittern (mass ratio)=mix 1:0.8～1.6, then spontaneous evaporation, precipitated sodium chloride and magnesium sulfate, as K in bittern
+content (mass ratio) is 3.2%～3.5%, Mg
2+when content (mass percent) is 5.0%～5.5%, separate sodium-chlor and magnesium sulfate, obtain potassium saturated bittern;
3. by the evaporation of potassium saturated bittern, solid is separated out, K in bittern
+content (mass ratio) is 2.0%～2.5%, Mg content (mass ratio) is while being 5.0%～7.5%, point isolated solid and remaining liq, and solid is potassium mixed salt, remaining liq is for analysing potassium mother liquor.
2. utilize according to claim 1 the method for producing potassium ores containing the magnesium sulfate bittern of nitrate, be characterised in that: described intercrystalline bittern passes through evaporation concentration in sodium salt field; Described high-sulfur bittern imports equalizing tank, is blended into and analyses potassium bittern, spontaneous evaporation, and precipitated sodium chloride and magnesium sulfate, obtain potassium saturated bittern; Described potassium saturated bittern is imported into the pond spontaneous evaporation of potassium mixed salt and analyses potassium.
3. utilize according to claim 1 the method for producing potassium ores containing the magnesium sulfate bittern of nitrate, be characterised in that: described in analyse potassium bittern for analysing potassium mother liquor, or make as follows analyse potassium bittern:
Get magnesium sulfate intercrystalline bittern spontaneous evaporation that six-membered system contains nitrate to the bittern of liquid phase containing potassium 2%, the freezing 48h that is no less than below-5 ℃, then solid-liquid separation, separating obtained liquid is for freezing bittern after nitre; After freezing nitre, bittern evaporation is concentrated, is evaporated to liquid phase containing potassium 3.6%～3.9%, Mg
2+content (mass percent) is 4.2%～4.8%, solid-liquid separation, and separating obtained liquid is high potassium bittern one; By high potassium bittern one evaporation concentration, be evaporated to liquid phase containing potassium 2.0-2.5%(mass percent again), carry out solid-liquid separation, gained solid is potassium mixed salt, separating obtained liquid is for analysing potassium bittern.
4. utilize according to claim 1 the method for producing potassium ores containing the magnesium sulfate bittern of nitrate, be characterised in that: described in analyse potassium bittern for analysing potassium mother liquor, or make as follows analyse potassium bittern: get magnesium sulfate intercrystalline bittern spontaneous evaporation that six-membered system contains nitrate to liquid phase containing potassium 3.9%(mass percent), then carry out solid-liquid separation, separating obtained liquid phase is high potassium bittern two, high potassium bittern two is continued to spontaneous evaporation and analyse potassium, be evaporated to liquid phase containing potassium 2.3%, again carry out solid-liquid separation, separating obtained liquid phase is for analysing potassium bittern.
5. utilize magnesium sulfate intercrystalline bittern that six-membered system contains nitrate to produce the method for saltpetre, comprise the following steps:
1. the method for producing potassium ores and production saltpetre by utilization claimed in claim 1 containing the magnesium sulfate bittern of nitrate is prepared potassium mixed salt;
2. potassium mixed salt purification removal of impurities: above-mentioned potassium mixed salt is carried out to ball milling in the ratio batching of solid-liquid mass ratio 1:2～4, and the liquid of solid-liquid batching use is flotation mother liquor, and the slip after ball milling first sieves, and screen overflow major ingredient is epsom salt; Screen underflow is carried out to flotation, and flotation reagent is selected hydrochloric acid stearylamine, the foam on liquid level is scraped with scraping plate of flotation machine, obtains flotation froth and flotation mother liquor;
3. saltpetre is refining: in the flotation froth obtaining to the removal of impurities of above-mentioned potassium mixed salt, add cold analysis mother liquor thermosol, thermosol temperature is controlled at 50 ℃～115 ℃, and the add-on of cold analysis mother liquor is by the K in hot solution
+content control, controls K in hot solution
+content is in 18%～28%(mass percent), then insulation separates, and separate solid is called high temp. salt, and separating liquid is called hot solution; The cooling rear solid-liquid separation of hot solution obtains separating out content 95%(mass percent) above Temperature and cold analysis mother liquor;
By Temperature: crystalline mother solution (mass ratio)=1:0.7～1 adds crystalline mother solution in above-mentioned Temperature, normal temperature washing separated after 30 minutes, and separating and obtaining solid is smart potassium, and separating and obtaining liquid is thick potassium washings; In smart potassium, add fresh water by the mass ratio of 1:0.4～0.43, thermosol at 100 ℃～110 ℃, after the pressure of thermosol liquid is cooling, separating out solid is the wet product of saltpetre, liquid is crystalline mother solution.
6. utilize according to claim 5 the magnesium sulfate intercrystalline bittern that contains nitrate to produce the method for saltpetre, be characterised in that: carry out drip washing to high temp. salt surface sprinkling fresh water, use fresh water agitator treating at 50 ℃～80 ℃, the add-on of fresh water is to wash the K in rear high temp. salt again
+content is less than 1.0%(mass percent) control, then separate, salt lake intercrystalline bittern pulp washing for separating obtained solid, then solid, liquid separation, separating obtained solid major ingredient is sodium-chlor and sodium sulfate; The liquid phase separating is washings, mixes rear evaporation with leacheate, superfluous cold analysis liquid, thick potassium washings, and blending proportion is to mix K in rear mixed solution
+: NO
3 -ratio (mass ratio) control, control K in mixed solution
+: NO
3 -=1:1.6～2.4, are evaporated to liquid phase containing K by mixed solution
+in 18%～28%(mass percent), then the hot solution of being returned in saltpetre refining step is incubated separation.
7. utilize according to claim 5 the magnesium sulfate intercrystalline bittern that contains nitrate to produce the method for saltpetre, be characterised in that: by wet described saltpetre product drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109319809A (en) * | 2018-12-04 | 2019-02-12 | 青海盐湖工业股份有限公司 | A kind of reverse flotation tail salt recovery processing method and system |
| CN110963511A (en) * | 2019-11-27 | 2020-04-07 | 新疆硝石钾肥有限公司 | System and method for producing optical glass-grade potassium nitrate by using sodium nitrate high-temperature mother liquor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB188634A (en) * | 1921-11-07 | 1923-12-05 | Guggenheim Brothers | Methods and processes for the leaching of caliche and for the recovery of nitrate therefrom |
| CN1439602A (en) * | 2002-09-25 | 2003-09-03 | 新疆罗布泊钾盐科技开发有限责任公司 | Preparation of potassium sulfate from brine containing potassium magnesium sulfate |
| CN1548372A (en) * | 2003-05-23 | 2004-11-24 | 中国科学院青海盐湖研究所 | Potassium sulfate preparing process from sulfate-type salt lake bittern |
| CN102838139A (en) * | 2012-10-09 | 2012-12-26 | 新疆安华矿业投资有限公司 | Method for producing potassium nitrate by utilizing salt lake brine in brine mixing mode |
-
2013
- 2013-07-02 CN CN201310274201.6A patent/CN103771460B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB188634A (en) * | 1921-11-07 | 1923-12-05 | Guggenheim Brothers | Methods and processes for the leaching of caliche and for the recovery of nitrate therefrom |
| CN1439602A (en) * | 2002-09-25 | 2003-09-03 | 新疆罗布泊钾盐科技开发有限责任公司 | Preparation of potassium sulfate from brine containing potassium magnesium sulfate |
| CN1548372A (en) * | 2003-05-23 | 2004-11-24 | 中国科学院青海盐湖研究所 | Potassium sulfate preparing process from sulfate-type salt lake bittern |
| CN102838139A (en) * | 2012-10-09 | 2012-12-26 | 新疆安华矿业投资有限公司 | Method for producing potassium nitrate by utilizing salt lake brine in brine mixing mode |
Non-Patent Citations (1)
| Title |
|---|
| 张占良: "用相图理论浅析盐湖卤水生产硝酸钾的工艺", 《盐业与化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109319809A (en) * | 2018-12-04 | 2019-02-12 | 青海盐湖工业股份有限公司 | A kind of reverse flotation tail salt recovery processing method and system |
| CN109319809B (en) * | 2018-12-04 | 2021-03-09 | 青海盐湖工业股份有限公司 | Reverse flotation tail salt recycling method and system |
| CN110963511A (en) * | 2019-11-27 | 2020-04-07 | 新疆硝石钾肥有限公司 | System and method for producing optical glass-grade potassium nitrate by using sodium nitrate high-temperature mother liquor |
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