CN103771460B - 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 one utilizes containing Na
+, K
+, Mg
2+/ Cl
-, SO
4 2-, NO
3 -isoionic six-membered system intercrystalline bittern (the magnesium sulfate salt lake intercrystalline bittern namely containing nitrate contains the magnesium sulfate intercrystalline bittern of nitrate also known as the magnesium sulfate bittern or six-membered system that contain nitrate) is by spontaneous evaporation, the method converting the higher potassium ores of operation solarization potassium nitrate content processed such as halogen, production saltpetre.
Background technology
Xinjiang is the area that China uniquely has containing saltpetre solid and liquid ore resources, utilizes this resource to produce saltpetre, no matter from locality or from national development, significant.Na is rich in kentite stone ore and salt lake intercrystalline bittern
+, K
+, Mg
2+, Cl
-, SO
4 2-, NO
3 -and the iodine of trace and boron, it can the natural high-quality saltpetre of processing, this product is in China and all belong to product in short supply in the world, 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 first carries out the leaching of ore, and leaching liquid salt pan is tedded, and 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 is substantially identical with solid mineral, is namely first tedded by salt pan in liquid ore deposit, desalination produces saltpetre work in-process, then carry out precision work; Because the ratio of component solid mineral in liquid ore deposit is complicated, utilize in process at actual development, the exploitation in liquid ore deposit, utilize difficulty much larger than the exploitation of solid mineral, utilization.
Bittern no matter after the molten leaching of solid mineral or intercrystalline bittern liquid ore deposit, when work in-process-potassium mixed salt is produced in spontaneous evaporation, part K
+with Mg
2+, SO
4 2-separate out, to K with Multiple salts forms
+recovery and improve K
+added value brings very large difficulty, and the solution of many investigators to it mainly contains two kinds of ways, a kind of be using lime as demagging agent in former halogen stage demagging by the Mg in brine deposit
2+, SO
4 2-removing, and then tedded by salt pan, desalination produces containing Mg
2+, SO
4 2-lower work in-process-potassium mixed salt, this method needs a large amount of lime, adds the production cost of product undoubtedly, moreover, Mg
2+, SO
4 2-the CaSO generated with lime reaction
4with Mg (OH)
2be difficult to recycle, and long-term external in a large number, the pollution of environment certainly will be caused, and the sodium-chlor that salt pan is separated out also is polluted by calcium sulfate, limits the use value of byproduct sodium-chlor.Another be with saltcake as demagging agent by the Mg in brine deposit
2+, SO
4 2-removing, specifically former halogen adds saltcake again by high temperature evaporation, and precipitation vanthoffite and vanthoffite remove Mg
2+, SO
4 2-; This method needs outsourcing saltcake, moreover high temperature evaporation also needs power consumption, adds 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 of magnesium sulfate intercrystalline bittern that effectively can solve six-membered system and contain nitrate, conventional spontaneous evaporation, shine Mg in the potassium ores of system
2+, SO
4 2-the problem that content is too high, by converting halogen, salt is analysed in segmentation, produce 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 magnesium sulfate bittern containing nitrate to produce the method for potassium ores, comprise the following steps:
1. six-membered system is contained the magnesium sulfate intercrystalline bittern of nitrate by evaporation concentration, separate out abraum salt, K in bittern
+when content (mass ratio) is 2.0% ~ 3.2%, is separated abraum salt, obtains high-sulfur bittern;
2. halogen is converted: by high-sulfur bittern: analyse potassium bittern (mass ratio)=1:0.8 ~ 1.6 and mix convert halogen mixed solution, then spontaneous evaporation, precipitated sodium chloride and magnesium sulfate, K to bittern
+content (mass percent) is 3.2% ~ 3.5%, Mg
2+when content (mass percent) is 5.0% ~ 5.5%, Isolating chlorinated sodium and magnesium sulfate, obtain potassium saturated bittern;
3. evaporated by potassium saturated bittern, solid is separated out, K in bittern
+when content (mass ratio) is 2.0% ~ 2.5%, Mg content (mass ratio) is 5.0% ~ 7.5%, point isolated solid and remaining liq, solid is potassium mixed salt, and remaining liq is for analysing potassium mother liquor.
onstate the method utilizing the magnesium sulfate bittern containing nitrate to produce potassium ores: 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, 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 utilizing and produce potassium ores containing the magnesium sulfate bittern of nitrate: described in analyse potassium bittern for analysing potassium mother liquor, or obtainedly 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%, freezingly below-5 DEG C be no less than 48h, then solid-liquid separation, separating obtained liquid is for freezing bittern after nitre; After freezing nitre, bittern evaporation concentrates, and 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; Again by high potassium bittern one evaporation concentration, be evaporated to liquid phase containing potassium 2.0-2.5%(mass percent), carry out solid-liquid separation, gained solid is potassium mixed salt, and separating obtained liquid is for analysing potassium bittern.
Above-mentioned utilization produces the method for potassium ores containing the magnesium sulfate bittern of nitrate, be characterised in that: described in analyse potassium bittern for analysing potassium mother liquor, or obtainedly 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 solid-liquid separation is carried out, separating obtained liquid phase is high potassium bittern two, high potassium bittern two is continued spontaneous evaporation and analyses 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.
Utilize the magnesium sulfate intercrystalline bittern containing nitrate to produce the method for saltpetre, comprise the following steps:
1. the method producing potassium ores by utilization according to claim 1 containing the magnesium sulfate bittern of nitrate prepares potassium mixed salt;
2. potassium mixed salt purification removal of impurities: above-mentioned potassium mixed salt is carried out ball milling in solid-liquid mass ratio 1:2 ratio batching, the liquid of solid-liquid batching is flotation mother liquor, and the slip after ball milling first sieves, and screen overflow major ingredient is epsom salt; Carry out flotation to screen underflow, hydrochloric acid stearylamine selected by flotation reagent, scraped by the foam on liquid level with scraping plate of flotation machine, obtains flotation froth and flotation mother liquor;
3. saltpetre is refined: in the flotation froth that the removal of impurities of above-mentioned potassium mixed salt obtains, add cold analysis mother liquor thermosol, and thermosol temperature controls at 50 DEG C ~ 115 DEG C, and the add-on of cold analysis mother liquor is by the K in hot solution
+content controls, and controls K in hot solution
+content is in 18% ~ 28%(mass percent), be then incubated separation, separate solid is called high temp. salt, and separating liquid is called hot solution; After hot solution cooling, solid-liquid separation obtains containing saltpetre 95%(mass percent) more than 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 washs after 30 minutes and is separated, and being separated and obtaining solid is smart potassium, and being separated 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 DEG C ~ 110 DEG C, after thermosol liquid forces cooling, separating out solid is that saltpetre wets product, and liquid is crystalline mother solution.
above-mentionedthe magnesium sulfate intercrystalline bittern containing nitrate is utilized to produce the method for saltpetre: carry out drip washing to high temp. salt surface sprinkling fresh water, then use fresh water agitator treating at 50 DEG C ~ 80 DEG C, 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 drip washing separation is carried out, the separating obtained liquid of drip washing is leacheate, drip washing separating obtained solid salt lake intercrystalline bittern pulp washing, carry out solid, liquid separation of sizing mixing again, the separating obtained solid major ingredient of solid, liquid of sizing mixing is sodium-chlor and sodium sulfate; The liquid phase that solid, liquid of sizing mixing is separated is washings, and mix rear evaporation with leacheate, superfluous cold analysis liquid, thick potassium washings, 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 returned in saltpetre refining step carries out insulation separation.
above-mentionedutilize the magnesium sulfate intercrystalline bittern containing nitrate to produce the method for saltpetre, wet described saltpetre product drying.
Beneficial effect 1. utilizes the method for producing potassium mixed salt containing the magnesium sulfate intercrystalline bittern of nitrate and nitric acid salt form bittern in the past to produce compared with saltpetre Technology, does not need to add any demagging agent.
2. halogen technology is converted in ingenious employing, the bittern after converting halogen is formed and enters the saturated phase region of epsom salt, avoid potassium magnesium sulfate double salt phase region; Due to common-ion effcet effect, separate out part epsom salt and sodium-chlor instantaneously, 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, turn avoid the precipitation in advance containing potassium double salt, substantially increase the yield of potassium and the quality of potassium mixed salt.The magnesium sulfate intercrystalline bittern that six-membered system contains nitrate eliminates magnesium sulfate by adopting the mode converting halogen, avoids the mode adopting high temperature evaporation in the past or add demagging agent removing magnesium sulfate.
3.
the major advantage of this method to adopt salt pan spontaneous evaporation, makes full use of local unique physical environment and weather condition, changes and adopt 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 obtained, the intermediates that the Technology in past is obtained after being evaporated by salt pan are potassium saturated bitterns, potassium saturated bittern produces saltpetre by workshop forced evaporation, and original process energy consumption is high, equipment corrosion is serious.
Magnesium sulfate intercrystalline bittern that six-membered system contains nitrate is utilized 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, merely add the hydrophobicity on potassium nitrate crystals surface and make potassium nitrate crystals swim on liquid level, other salt then sinks to bottom flotation cell, by scraping plate of flotation machine, foam is scraped, achieve being separated of saltpetre and other salt; The saltpetre of flotation froth mainly containing a small amount of sodium-chlor, magnesium sulfate, 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 nitric acid salt form 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 scale development crow brave Bu Lake salt lake six-membered system contains nitrate.
Potassium bittern of analysing of the present invention refers to and analyses K after potassium
+content (mass ratio) is 2.0% ~ 2.5%, Mg content (mass ratio) is the bittern of 5.0% ~ 7.5%.
Of the present invention
analyse potassium mother liquor:the bittern that sodium-chlor, magnesium sulfate, saltpetre and carnallitite are saturated altogether;
Of the present invention
high-sulfur bittern:the bittern that sodium-chlor, saltcake and potassium magnesium sulfate double salt are saturated altogether;
Of the present invention
high potassium bittern one: the bittern that sodium-chlor, magnesium sulfate and saltpetre are saturated 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 magnesium sulfate bittern containing nitrate to produce potassium ores and produces the schema of saltpetre.
Embodiment
following embodimentsalt lake used intercrystalline bittern takes 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 slightly fluctuates).
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 one:
1. potassium mixed salt is produced:
Single stage desalting: get black honor Bu Lake salt lake intercrystalline bittern 1000Kg, being placed on multiple bore is 50cm, the degree of depth is in the plastic tub of 20cm, concentrates in laboratory spontaneous evaporation, is evaporated to liquid phase containing potassium 1.27%, be separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase referred to herein as sodium-chlor, sodium chloride content reaches more than 95%, meets Industrial Salt service requirements completely, be separated liquid phase referred to herein as sodium sulfate saturated bittern, it proceeds spontaneous evaporation concentrating and desalinating.
Secondary desalination: sodium sulfate saturated bittern being placed in multiple bore is 50cm, the degree of depth is in the plastic tub of 20cm, concentrate in spontaneous evaporation, be evaporated to liquid phase containing potassium 2.05%, be separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase referred to herein as abraum salt, it is the mixture of sodium sulfate and sodium-chlor, being separated 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, separate out a small amount of sodium-chlor and magnesium sulfate instantaneously simultaneously, mix liquid referred to herein as converting saltwater brine, then converting saltwater brine, to be placed in multiple bore be 50cm, the degree of depth is in the plastic tub of 20cm, concentrate in laboratory spontaneous evaporation, be evaporated to liquid phase containing potassium 3.25%, be separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase referred to herein as epsom salt, it is mainly the mixture of magnesium sulfate heptahydrate and sodium-chlor, being separated liquid phase is potassium saturated bittern, it carries out spontaneous evaporation and analyses potassium.
analyse potassium:potassium saturated bittern being placed in multiple bore is 50cm, 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%, is separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase referred to herein as potassium mixed salt, it is the mixture of potassium nitrate containing a small amount of magnesium sulfate heptahydrate, sodium-chlor, and be separated liquid phase for analysing potassium mother liquor, 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 contains potassium 2% bittern to liquid phase, being contained in multiple bore is 47cm*35cm, the degree of depth is in the plastic tub of 40cm, in family expenses Haier refrigerator-freezer, freezing 48h below-5 DEG C, then be separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase referred to herein as ice nitre, it is mainly the sal glauberi containing a small amount of sodium-chlor, be separated liquid phase for freezing bittern after nitre, after freezing nitre, bittern is placed in multiple bore is 50cm, the degree of depth is in the plastic tub of 20cm, concentrate in laboratory spontaneous evaporation, be evaporated to liquid phase containing potassium 3.9%, Mg
2+when content (mass percent) is 4.45%, be separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase and be mainly sodium-chlor, being separated liquid phase is high potassium bittern one, again high potassium bittern one being placed in multiple bore is 50cm, the degree of depth is in the plastic tub of 20cm, concentrate in laboratory spontaneous evaporation, be evaporated to liquid phase containing potassium 2.3%, be separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase and be also referred to as-potassium mixed salt at this, it is the mixture of potassium nitrate containing a small amount of magnesium sulfate heptahydrate, sodium-chlor, and it is the raw material producing saltpetre, be separated liquid phase for analysing potassium mother liquor, it converts halogen process raw brine as above-mentioned.
In this process, main material data and content thereof show in table 2.
Table 2: potassium mixed salt producing process stage each material data 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, QM (0 ~ 5L) laboratory tumbling ball mill is used to carry out ball milling at twice, Ball-milling Time is 20min, originally mother liquor fresh water, and Posterior circle uses;
screening:slip after ball mill ore grinding 60 mesh standard sieves sieve, and a small amount of flotation mother liquor of on-the-sieve material rinses, and screen overflow is referred to herein as epsom salt, and it is mainly the magnesium sulfate heptahydrate containing 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 prepared) flotation reagent 5ml, mixing 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 centrifuge dewatering, be mainly containing 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 being separated, liquid phase is flotation mother liquor, it recycles,
flotation salt process:flotation residue slip XS200-2.8L whizzer is separated, 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, be separated 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, be separated liquid phase referred to herein as returning solution one, its component concentration reaches the sodium sulfate saturated bittern component concentration of operation 1. single stage desalting process, it is directly returned secondary demineralising process to recycle.
1. operation is analysed the potassium mixed salt 10.51Kg of potassium process output by after above-mentioned steps gradation, circular treatment, in process, each main material integrated data and content thereof show in table 3.
Table 3: potassium mixed salt dedoping step stage each material data and content thereof
Table 3: potassium mixed salt dedoping step stage each material data and content thereof
3. saltpetre is refined:
thermosol removal of impurities:get the operation 2. flotation froth 0.6Kg that obtains of floatation process, 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 controls at 105 DEG C, and the add-on of cold analysis mother liquor is by the K in hot solution
+content controls, and controls K in hot solution
+content is 23%, after being heated to 105 DEG C, insulated and stirred 5min, then SHZ-D III water circulating type vacuum pump suction filtration is used, by 2500ml filter flask and the boiling preheating in the hot water of ￠ 210 Büchner funnel 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 is separated, liquid is referred to herein as high-temperature liquid, high-temperature liquid is used for crystallisation by cooling, separate solid is high temp. salt, for high temp. salt drip washing, (thermosol temperature controls 50 DEG C ~ 115 DEG C differences according to lectotype selection in washing, select different control temperature, temperature is higher, yield is higher, 115 DEG C of boiling points close to hot solution).
high temp. salt drip washing, washing: a small amount of fresh water of high temp. salt surface sprinkling in the isolated rear Büchner funnel of thermosol dedoping step, use SHZ-D III water circulating type vacuum pump suction filtration simultaneously, fresh water fountain height sprays one time with high temp. salt surface uniform and is as the criterion, parting liquid is leacheate, it is inserted 2000ml beaker and stores, to mother liquid evaporation process, separate solid is drip washing solid, inserted 500ml beaker, add appropriate fresh water, stir, at the heating by electric cooker of 1000W with JJ-1 type experiment electric mixer, wash temperature is 80 DEG C, and the add-on of fresh water is to wash the K in rear high temp. salt
+content is less than 1% control, washing slip SHZ-D III water circulating type vacuum pump suction filtration, separating liquid is referred to as high temp. salt washings at this, itself and leacheate above together store, 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, be separated 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, be separated liquid phase referred to herein as returning solution two, its component concentration reaches the sodium sulfate saturated bittern component concentration of operation 1. single stage desalting process substantially, it is directly returned secondary demineralising process to recycle.
crystallisation by cooling:high-temperature liquid after being separated by thermosol dedoping step suction filtration 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 DEG C, then be separated with XS200-2.8L experiment whizzer, separate solid is referred to herein as Temperature, its purity reaches more than 95%, carry out thick potassium washing to Temperature, separating liquid is cold analysis mother liquor, the most of molten dedoping step that reduces phlegm and internal heat that circulates of cold analysis mother liquor, residue cold analysis mother liquor and above leacheate together store, to mother liquid evaporation process.
thick potassium washing:the Temperature that crystallisation by cooling process obtains is inserted 1000ml beaker, add a small amount of thick potassium washings of fresh water or crystalline mother solution and last time simultaneously, (use fresh water at first, the crystalline mother solution with finishing operations has been opened) with Posterior circle, additional proportion is Temperature: the mass ratio=1:0.9 of mother liquor, in normal temperature JJ-1 type experiment electric mixer agitator treating 30 minutes, then be separated 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, remain thick potassium washings together to store with leacheate above, to mother liquid evaporation process.
recrystallization:thick potassium is washed the smart potassium obtained and inserts 1000ml beaker, fresh water is added 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 controls at 110 DEG C, cold water indirect heat exchange is used after dissolving completely, force cooling, stir with JJ-1 type experiment electric mixer simultaneously, until high-temperature liquid temperature is cooled to 25 DEG C, then be separated 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 obtained by recrystallization is laid in the enamel pallet of 300mm*200mm, inserts in 101-1 type Constant Temp. Oven, dry 60min at 105 DEG C, and after dry, material is the technical grade premium grads potassium nitrate 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 2000ml beaker, stirs with JJ-1 type experiment electric mixer, evaporate at the heating by electric cooker of 1000W, be evaporated to mixed solution liquid phase containing K
+23%, return it to the separating step of this operation thermosol dedoping step, repeat above process.
By the flotation froth 4.91Kg of operation 2. floatation process output by above-mentioned steps gradation, after circular treatment, in process, each main material integrated data and content thereof show in table 4.
Table 4: saltpetre treating process stage each material data and content thereof
Table 4: saltpetre treating process stage each material data and content thereof
By this technique, utilizing crow brave Bu Lake salt lake intercrystalline bittern to produce saltpetre executes feasible, can 63.6% be arrived 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 crow brave Bu Lake salt lake intercrystalline bittern amount.
This technological process output saltpetre is pressed GB 1918-2011 industrial potassium nitrate standard and is performed, and indices measures situation in table 5.
Table 5: this technological process output saltpetre indices measures situation
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, be dissolved completely in after in concentrated hydrochloric acid until stearylamine, then add the hot water being not less than 60 DEG C the content of hydrochloric acid stearylamine is diluted to 2%(mass percent).
The using method of flotation reagent: potassium mixed salt slip is imported in flotation machine, add the flotation reagent prepared by following dosage simultaneously, stirred by flotation machine main shaft, flotation reagent is made to intersperse among inside potassium mixed salt slip uniformly, do not stop to blast air in slip with flotation machine air pump simultaneously, the flotation reagent surface tension being attached with potassium nitrate crystals increases, generation foaming moves upward, potassium nitrate crystals is made to swim on potassium mixed salt slip table liquid level, other salt then sinks to bottom flotation cell, by scraping plate of flotation machine, the potassium nitrate crystals swum on potassium mixed salt slip table liquid level is scraped, achieve being separated of saltpetre and other salt.
The consumption of flotation reagent: the consumption of stearylamine controls according to the height of potassium content in potassium mixed salt, and namely potassium mixed salt potassium content is higher, then unit potassium mixed salt consumes the quantity just corresponding increase of stearylamine.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.
willpotassium mixed salt slip
putenter X-d III-3L unit flotation cell
in, add the flotation reagent prepared in proportion simultaneously,
pass throughflotation machine main shaft stirs, and makes flotation reagent intersperse among inside potassium mixed salt slip uniformly,
andbe attached to potassium nitrate crystals surface, add the hydrophobicity on potassium nitrate crystals surface,
simultaneouslyflotation machine air pump does not stop to blast air in slip,
the flotation reagent surface tension being attached with potassium nitrate crystals increases, and produces foaming and moves upward,potassium nitrate crystals is swum in
potassium mixed salt slip tableon liquid level, other salt then sinks to bottom flotation cell, will be swum in by scraping plate of flotation machine
potassium mixed salt slip tablepotassium nitrate crystals on liquid level scrapes, and achieves being separated of saltpetre and other salt.
Adopt concentrated hydrochloric acid to dissolve stearylamine faster than employing diluted hydrochloric acid dissolution stearylamine dissolution rate, reaction thoroughly.
In the above-described embodiments, rear evaporation mixed by the washings be separated in saltpetre purification step and leacheate, superfluous cold analysis liquid, thick potassium washings, 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 is 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, regulate and control the liquid phase potassium ion in evaporative process, solid content, higher than 60%, suitably turns down the concentration of evaporation liquid phase potassium ion, and solid content, lower than 30%, suitably can heighten the concentration of evaporation liquid phase potassium ion), return it to this operation hot solution and carry out insulation separation, repeat above process.
describedin purity more than 95% Temperature, add crystalline mother solution, additional proportion is Temperature: mass ratio=1:0.7 ~ 1 of crystalline mother solution
(wash concentration controls below 60%, can ensure that material fully stirs with slurry state, and can ensure the washing effect of impurities ion in Temperature), be separated after normal temperature washs 30 minutes, separate solid is smart potassium, carries out recrystallization to smart potassium, and separating liquid is thick potassium washings, and it is to evaporation; Fresh water is added by the mass ratio of 1:0.4 ~ 0.43, at 100 DEG C ~ 110 DEG C in smart potassium
(solubleness of saltpetre increases along with the rising of temperature, and the boiling point of saltpetre saturated solution can also reach 113 DEG C at ambient pressure, and lower in this solvent temperature, amount of water certainly will increase, and yield certainly will reduce; Simultaneously for ensureing recrystallization product quality, in actual mechanical process, according to smart potassium impurity ion content, adjustable recrystallization process amount of water, make it thermosol under corresponding temperature of saturation, namely smart potassium impurity ion content is relatively higher, and we can increase recrystallization amount of water, and such thermosol temperature can correspondingly decline; Essence potassium impurity ion content is relatively on the low side, and we can reduce recrystallization amount of water, the corresponding rising of such thermosol temperature)lower thermosol, after thermosol liquid forces cooling (use tap water circulating cooling), separating out solid is that saltpetre wets product, and after drying, be the technical grade premium grads saltpetre that purity is greater than 99.7%, liquid is crystalline mother solution, and it removes washing Temperature.
In above-described embodiment,
in the secondary desalting steps that potassium mixed salt is produced,sodium sulfate saturated bittern is evaporated to liquid phase containing potassium (mass ratio)
2.0% ~ 3.2% all can meeting tier 2 desalination, the requirement of converting halogen, analysing potassium process.liquid phase containing potassium (mass ratio) higher than
when 3.2%, potassium ion will be separated out in advance, will containing sylvite in abraum salt, then 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
when 2.0%, sodium sulfate is separated out and will not exclusively, be caused 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
the Con trolling index of ~ 1.6 all can meet the requirement of converting halogen, analysing potassium process, but this ratio higher than1:0.8 time
, follow-up potassium process of analysing separates out that potassium mixed salt quantity reduces to some extent, potassium yield reduces relatively; After controlling to this indicator conditions, 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
any order number standard sieve screening, all can realize the object of sieving, select different screening order numbers, epsom salt screening effect is by difference.
In above-described embodiment,
in high temp. salt drip washing in saltpetre is refined, washing step,wash temperature general control at 50 DEG C ~ 80 DEG C,
the potassium ion contained in high temp. salt after drip washing mainly exists with kainite form, and select this temperature range, object is potassium ion and nitrate ion are fully transformed, potassium ion is made to enter liquid phase, be convenient to reclaim, the too low conversion being unfavorable for potassium ion of temperature, the too high heat energy consumption of temperature is high.
embodiment two:just be with the difference of embodiment one, in embodiment one operation 1. in the middle of convert halogen process, high-sulfur bittern: the mass ratio of analysing potassium bittern is 1:0.8, and in the present embodiment, this ratio is in high-sulfur bittern: the mass ratio of analysing potassium bittern be situation after the ratio of 1:1.6 is carried out as following:
Convert halogen: by high-sulfur bittern: the mass ratio of analysing potassium bittern is 1:1.6, mix and mix, separate out a small amount of sodium-chlor and magnesium sulfate instantaneously simultaneously, mix liquid referred to herein as converting saltwater brine, then converting saltwater brine, to be placed in multiple bore be 50cm, the degree of depth is in the plastic tub of 20cm, concentrate in laboratory spontaneous evaporation, be evaporated to liquid phase containing potassium 3.36%, be separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase referred to herein as epsom salt, it is mainly the mixture of magnesium sulfate heptahydrate and sodium-chlor, being separated liquid phase is potassium saturated bittern, adopt spontaneous evaporation mode to evaporate to potassium saturated bittern and analyse potassium.
With high-sulfur bittern after converting halogen 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 in spontaneous evaporation process, separate out the quantity of epsom salt, evaporation duration corresponding minimizing, shortening, potassium saturated bittern analyses the corresponding minimizing of potassium mixed salt quantity of output in potassium process in later stage spontaneous evaporation.
After being implemented by the present embodiment, potassium mixed salt producing process stage each material data and content thereof are in table 6.
Table 6: potassium mixed salt producing process stage each material data and content thereof
embodiment three:just be with the difference of embodiment one, in embodiment one operation 1. in the middle of convert halogen with analysing potassium mother liquor preparation process bittern used containing potassium 2%, convert in the present embodiment 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 contains potassium 2.38% bittern to liquid phase, being contained in multiple bore is 47cm*35cm, the degree of depth is in the plastic tub of 40cm, in family expenses Haier refrigerator-freezer, at-8 DEG C of freezing 48h, then be separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase referred to herein as ice nitre, it is mainly the sal glauberi containing a small amount of sodium-chlor, be separated liquid phase for freezing bittern after nitre, after freezing nitre, bittern is placed in multiple bore is 50cm, the degree of depth is in the plastic tub of 20cm, concentrate in laboratory spontaneous evaporation, be evaporated to liquid phase containing potassium 3.66%, Mg
2+when content (mass percent) is 4.53%, be separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase and be mainly sodium-chlor, being separated liquid phase is high potassium bittern one, again high potassium bittern one being placed in multiple bore is 50cm, the degree of depth is in the plastic tub of 20cm, concentrates in laboratory spontaneous evaporation, is evaporated to liquid phase containing potassium 2.17%, Mg
2+content (mass percent) is 7.22%, is separated with the link-suspended basket centrifuge that rotary drum is 40cm, is separated solid phase and is also referred to as-potassium mixed salt at this, and it is the mixture of potassium nitrate containing a small amount of magnesium sulfate heptahydrate, sodium-chlor, and it is the raw material producing saltpetre, be separated liquid phase for analysing potassium mother liquor, it converts halogen process raw brine as above-mentioned.Produce the essential distinction of analysing potassium mother liquor at the bittern in 2% and 2.% to 2.4% interval be just that the quantity separating out ice nitre in refrigerating process reduces to some extent by standby potassium mother liquor and the potassium content of analysing of the making from brine of this potassium content.
Table 7: analyse potassium bittern preparation process bittern content
embodiment four:just be with the difference of embodiment one, in embodiment one operation 1. in the middle of convert halogen 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 contains potassium more than 2% bittern to liquid phase, being placed on multiple bore is 50cm, and the degree of depth is in the plastic tub of 20cm, concentrates in laboratory spontaneous evaporation, is evaporated to liquid phase containing potassium to 3.96%, Mg
2+when content (mass percent) is 5.33%, be separated 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 Multiple salts forms exists and a large amount of sodium-chlor, discarded, being separated liquid phase is potassium saturated bittern, potassium saturated bittern being placed in multiple bore is 50cm, 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%, be separated with the link-suspended basket centrifuge that rotary drum is 40cm, be separated solid phase and be also referred to as assorted potassium mixed salt at this, they are a large amount of with potassium for containing, magnesium, several double salt that sulfate radical Multiple salts forms exists and sodium-chlor, the mixture of saltpetre, it is continued to employ, be separated liquid phase for analysing potassium bittern, it also can convert halogen process raw brine as above-mentioned.Can soak with former halogen after the assorted potassium mixed salt of separating out and dissolve, to reclaim the useful components such as potassium in assorted potassium mixed salt, the bittern after immersion again deduplication example one carries out the sequence of operations such as evaporation.
In process, output height potassium bittern two content shows in table 8.
Table 8: high potassium bittern two content
embodiment five:the basic skills of the present embodiment and step are with embodiment one, embodiment two, embodiment three, embodiment four difference:
The producing process of potassium mixed salt is realized by salt pan spontaneous evaporation.
Potassium mixed salt is produced:
Single stage desalting: get black honor Bu Lake salt lake intercrystalline bittern about 5000 tons, be placed on the pond spontaneous evaporation of one-level sodium to concentrate, 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 deposited, solid phase Ji Dui stores, and drop goes out bittern and imports secondary sodium pond in the lump.
Secondary desalination: the sodium sulfate saturated bittern that one-level sodium pond is imported, be placed in the pond spontaneous evaporation of secondary sodium to concentrate, 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 deposited, solid phase Ji Dui stores, and drop goes out bittern and imports bittern-mixing pool in the lump.
Convert halogen: the high-sulfur bittern imported in secondary sodium pond, be placed in bittern-mixing pool, simultaneously in high-sulfur bittern: the mass ratio of analysing potassium bittern is that the ratio of 1:0.9 imports and analyses potassium mother liquor and mix, mix liquid referred to herein as converting saltwater brine, it concentrates 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 deposited, solid phase Ji Dui stores, drop goes out bittern and imports sylvite pond in the lump.
Convert the halogen source of analysing potassium bittern: the intercrystalline bittern being stored in salt pan, black honor Bu Lake salt lake early stage, by the method for embodiment two, the bittern obtained in salt pan.
Analyse potassium: the potassium saturated bittern imported by bittern-mixing pool, 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, and be evaporated to liquid phase containing potassium 2.5%, 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 containing 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 deposited, solid phase Ji Dui stores, as the raw material producing saltpetre.
Obtained the potassium mixed salt of about 48 tons by above-mentioned potassium mixed salt producing process, its quality is better than the quality of the potassium mixed salt that embodiment one operating process obtains, and its data are in table 9.
Table 9: potassium mixed salt producing process obtains potassium mixed salt data
Can 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, precipitated sodium chloride and magnesium sulfate, must convert saltwater brine; Described convert saltwater brine be imported into potassium mixed salt pond evaporation analyse potassium.
above-mentionedutilize the magnesium sulfate intercrystalline bittern containing nitrate to produce the method for saltpetre, the wet saltpetre obtained by recrystallization is laid in enamel pallet, inserts in Constant Temp. Oven, and dry 60min at 105 DEG C, can obtain technical grade potassium nitrate product.
Describedly analyse potassium bittern, can obtain as follows respectively at the beginning of the cycle: get magnesium sulfate intercrystalline bittern spontaneous evaporation that six-membered system contains nitrate and concentrate to the bittern spontaneous evaporation of liquid phase containing potassium more than 2%, be evaporated to liquid phase containing potassium to 3.9%, then solid-liquid separation is carried out, separate solid is referred to herein as abraum salt, it is mainly with the double salt of potassium, magnesium, the existence of sulfate radical Multiple salts forms and a large amount of sodium-chlor, is discarded; Being separated liquid phase is potassium saturated bittern, potassium saturated bittern is continued spontaneous evaporation and analyses potassium, be evaporated to liquid phase containing potassium 2.3%, again carry out solid-liquid separation, be separated solid phase referred to herein as assorted potassium mixed salt, it be the mixture containing several double salt existed with potassium, magnesium, sulfate radical Multiple salts forms in a large number and sodium-chlor, saltpetre, and it soaks dissolving with salt lake intercrystalline bittern, reclaim the useful components such as the potassium in assorted potassium mixed salt, the bittern after immersion repeats spontaneous evaporation and concentrates; Be separated liquid phase for analysing potassium bittern, it also can convert halogen process raw brine as above-mentioned.
Claims (6)
1. utilize the magnesium sulfate bittern containing nitrate to produce the method for potassium ores, comprise the following steps:
1. six-membered system is contained the magnesium sulfate intercrystalline bittern of nitrate by evaporation concentration, separate out abraum salt, K in bittern
+when content mass ratio is 2.0% ~ 3.2%, is separated abraum salt, obtains high-sulfur bittern;
2. halogen is converted: by high-sulfur bittern: analyse potassium brine quality ratio=1:0.8 ~ 1.6 and mix, 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%, Isolating chlorinated sodium and magnesium sulfate, obtain potassium saturated bittern;
3. evaporated by potassium saturated bittern, solid is separated out, K in bittern
+when content mass ratio is 2.0% ~ 2.5%, Mg content mass ratio is 5.0% ~ 7.5%, point isolated solid and remaining liq, solid is potassium mixed salt, and remaining liq is for analysing potassium mother liquor;
Described potassium bittern of analysing for analysing potassium mother liquor, or obtainedly as follows analyses potassium bittern:
Get magnesium sulfate intercrystalline bittern spontaneous evaporation that six-membered system contains nitrate to the bittern of liquid phase containing potassium 2% mass ratio, freezingly below-5 DEG C be no less than 48h, then solid-liquid separation, separating obtained liquid is for freezing bittern after nitre; After freezing nitre, bittern evaporation concentrates, and 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; Again by high potassium bittern one evaporation concentration, be evaporated to liquid phase containing potassium 2.0-2.5% mass percent, carry out solid-liquid separation, gained solid is potassium mixed salt, and separating obtained liquid is for analysing potassium bittern.
2. utilize the magnesium sulfate bittern containing nitrate to produce the method for potassium ores according to claim 1, 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, 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 the method producing potassium ores containing the magnesium sulfate bittern of nitrate according to claim 1, be characterised in that: described in analyse that potassium bittern is obtained as follows analyses 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 solid-liquid separation is carried out, separating obtained liquid phase is high potassium bittern two, high potassium bittern two is continued spontaneous evaporation and analyses 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.
4. 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 potassium ores is produced containing the magnesium sulfate bittern of nitrate by utilization according to claim 1, obtained potassium mixed salt;
2. potassium mixed salt purification removal of impurities: above-mentioned potassium mixed salt is carried out ball milling in the ratio batching of solid-liquid mass ratio 1:2 ~ 4, and the liquid of solid-liquid batching is flotation mother liquor, and the slip after ball milling first sieves, and screen overflow major ingredient is epsom salt; Carry out flotation to screen underflow, hydrochloric acid stearylamine selected by flotation reagent, scraped by the foam on liquid level with scraping plate of flotation machine, obtains flotation froth and flotation mother liquor;
3. saltpetre is refined: in the flotation froth that the removal of impurities of above-mentioned potassium mixed salt obtains, add cold analysis mother liquor thermosol, and thermosol temperature controls at 50 DEG C ~ 115 DEG C, and the add-on of cold analysis mother liquor is by the K in hot solution
+content controls, and controls K in hot solution
+content, in 18% ~ 28% mass percent, is then incubated separation, and separate solid is called high temp. salt, and separating liquid is called hot solution; After hot solution cooling, solid-liquid separation obtains Temperature and the cold analysis mother liquor of separating out more than content 95% mass percent;
By Temperature: crystalline mother solution mass ratio=1:0.7 ~ 1 adds crystalline mother solution in above-mentioned Temperature, normal temperature washs after 30 minutes and is separated, and being separated and obtaining solid is smart potassium, and being separated 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 DEG C ~ 110 DEG C, after thermosol liquid forces cooling, separating out solid is that saltpetre wets product, and liquid is crystalline mother solution.
5. utilize the magnesium sulfate intercrystalline bittern containing nitrate to produce the method for saltpetre according to claim 4, be characterised in that: carry out drip washing to high temp. salt surface sprinkling fresh water, use fresh water agitator treating at 50 DEG C ~ 80 DEG C again, the add-on of fresh water is to wash the K in rear high temp. salt
+content is less than 1.0% mass percent and controls, and is then separated, separating obtained solid salt lake intercrystalline bittern pulp washing, then solid, liquid is separated, and separating obtained solid major ingredient is sodium-chlor and sodium sulfate; The liquid phase be separated is washings, and mix rear evaporation with leacheate, superfluous cold analysis liquid, thick potassium washings, 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 returned in saltpetre refining step carries out insulation separation.
6. utilize the magnesium sulfate intercrystalline bittern containing nitrate to produce the method for saltpetre according to claim 4, be characterised in that: wet described saltpetre product drying.
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| 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 |
| CN116040661B (en) * | 2023-01-18 | 2024-09-10 | 广东邦普循环科技有限公司 | Comprehensive utilization method of salt lake brine |
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