CN103570043B - Method for producing high-purity potassium chloride solution for preparation of potassium carbonate and co-producing low sodium salt - Google Patents
Method for producing high-purity potassium chloride solution for preparation of potassium carbonate and co-producing low sodium salt Download PDFInfo
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Abstract
The invention discloses a method for producing a high-purity potassium chloride solution for preparation of potassium carbonate and co-producing low sodium salt. The high-purity potassium chloride solution for producing potassium carbonate is prepared from agricultural grade potassium chloride serving as a raw material by the steps of rinsing, dissolving, removing impurities, settling, filtering and the like, wherein the Ca<2+> content is less than or equal to 0.0001%, the Mg<2+> content is less than or equal to 0.0001%, the Fe content is less than or equal to 0.0001%, the content of suspended solids (SS) is less than or equal to 0.1 mg/L, pH is 12+/-0.2, and the potassium chloride content is more than or equal to 99.0%, so the quality standard of an ion exchange method for producing the potassium carbonate is complete met. Potassium chloride rinsing liquid and leachate is recycled, evaporated and concentrated, and subjected to crystallization separation according to the dissolution characteristics of the potassium chloride and sodium chloride, the potassium chloride obtained by recycling can serve as the raw materials to be reused, and the mixture containing the potassium chloride and the sodium chloride meets the quality requirement of low sodium salt.
Description
Technical field
The present invention relates to field of inorganic chemical engineering, particularly relate to a kind of method of producing high purity potassium chloride needed for salt of wormwood and coproduction Cardia Salt.
Background technology
Salt of wormwood is important industrial chemicals, be widely used in the industries such as chemical industry, light industry, picture tube glass bulb, pharmacy, food, welding electrode and Non-ferrous Metallurgy, wide market, ion exchange method and ionic membrane-electrolytic process are the main method of producing salt of wormwood at present.Ion-exchange membrane electrolysis is by electrolytic chlorination potassium, first potassium hydroxide and by product chlorine is obtained, potassium hydroxide obtains salt of wormwood by carbonating again, and this technique has the advantages such as constant product quality and three-waste pollution are few, but very high to the specification of quality of raw material Repone K in production process, need from external import, this production technology is controlled by external major company simultaneously, needs from import equipment and technology, and investment radix is large, return period is long, and short duration, inherent China can not by spread.The processing method of method for producing potassium carbonate by ion exchange has the advantages such as the excellent and less investment of quality product, adopt by domestic most manufacturing enterprise, because once once being listed in superseded technique by National Development and Reform Committee because its three-waste pollution is serious and energy consumption is high, therefore domestic many enterprises stopped production and close or change the line of production.In recent years, by the research of technique of scientific research personnel, achieve ion-exchange closed cycle, solve three-waste pollution problem, in reducing energy consumption, also carried out large quantity research simultaneously, achieve notable results, state of the art and the ion-exchange membrane electrolysis gap of current ion exchange method constantly reduce, and product is occupied an leading position in market at home.
China is a large agricultural country, is also the country of a potash fertilizer famine, and in order to satisfy the demand, country will spend a large amount of foreign exchange from Israel, Canada and state's import potash fertilizer such as Russian every year.The potassium resource of China concentrates on the Cha Er Han Salt Lake in Qinghai mostly, and reserves are about 1.45 hundred million tons, and account for 97% of national proven reserve, country drops into huge fund and sets up KCl production line at Qinghai Salt Lake, alleviates the short present situation of domestic potash fertilizer in a way.The production of current Qinghai Salt Lake Repone K mainly through the natural bittern picking up from salt pan is shone carnallitite processed, then adopts reverse flotation-cooling and crystallizing process.In reverse flotation-cooling and crystallizing process, first with the sodium-chlor carried secretly in flotation reagent removing carnallitite, then add water selective dissolution magnesium chloride, after centrifugation, drying, namely obtain Potassium Chloride Product.This technology utilize flotation technology ingenious solve sodium-chlor and Repone K be separated a difficult problem, the extensive utilization for salt lake potassium resource opens a new way, also solves the shortage of China's Potassic fertilizer resources to a certain extent.But, containing the impurity such as a large amount of calcium sulfate and magnesium chloride in the salt lake brine that domestic current production Repone K is used, and Repone K is in state of saturation all the time and exists mainly with solid form in whole KCl production process, utilize existing technique cannot the impurity such as fully effective removal calcium sulfate wherein, magnesium chloride and sodium-chlor, the foreign matter content such as calcium sulfate and sodium-chlor in the Repone K of giving birth to now is caused to remain high, Repone K purity is mostly lower than 95%, and in quality and price, all difficulty and import high purity potassium chloride (KCE content >=98.0%) are competed.Use Klorvess Liquid to utilize method for producing potassium carbonate by ion exchange, the quality of its main raw material Repone K directly affects quality and the production cost of salt of wormwood, only has the quality of highly purified Repone K guarantee salt of wormwood.The higher-grade Repone K quality of external import is compared with domestic Repone K has very strong competitive edge, but Repone K price rises year by year in recent years, rise to 4000 yuan/ton at present, for beyond affordability salt of wormwood production industry, the significant technology issues how utilizing inexpensive domestic KCl production salt of wormwood to become current many salt of wormwood enterprises to be badly in need of solving.
In field of inorganic chemical engineering, from product, thoroughly removing calcium and magnesium are comparatively general technical barriers.General deliming adopts and adds precipitation agent (as vitriol, carbonate and oxalate etc.), calcium in solution is separated out with precipitation forms, demagging is also generally adopt to add precipitation agent (as the highly basic such as sodium hydroxide and potassium hydroxide), solution ph is adjusted to more than 10, and MAGNESIUM METAL ion is separated out with the form of magnesium hydroxide.And it is more strict to impurity control indexes such as calcium, magnesium and iron to produce Klorvess Liquid needed for salt of wormwood, require that the foreign matter contents such as calcium in Klorvess Liquid, magnesium and iron are less than 1ppm, conventional treatment method reaches very much.Chinese invention patent CN200210086474.3 provides a kind of calcium removing and purification method of industrial potassium chloride, it is characterized in that: described method employing thing phase inversion process substep removes the calcium sulfate impurity in industrial potassium chloride, first in the saturated Repone K aaerosol solution containing solid potassium chloride and solid calcium sulphate, calcium remover A is added, calcium sulfate in aaerosol solution is converted into the Ca-deposit that solubleness is lower, be more soluble in acid or complex compound, sulfate ion is entered in water and is removed by filter type; Then carry solid and add filtering institute the saturated potassium chloride solution newly prepared, add calcium remover B selective dissolution Ca-deposit, make calcium enter solution and cross to filter, reach deliming object thus, wherein calcium remover A is inorganic soluble acid carbonate or Soluble oxalate salt, and wherein calcium remover B is hydrochloric acid or nitric acid.Adopt the KCE content after described method process to reach 99%, calcium sulphate content is less than 1%, does not therefore also reach the specification of quality needed for method for producing potassium carbonate by ion exchange.
Chinese invention patent CN200410012535.7 provides a kind of method of refined brine, specifically a kind of method removing calcium in crude brine, magnesium ion acquisition refined brine.Concrete grammar is: be placed on by crude brine in demagging reactor, adds the settling agent PAM and milk of lime that prepare in reactor, reacts 0.5 hour obtained distiller liquor; A distiller liquor is put into primary brine settling tank clarify, obtained primary brine, a mud remaining at the bottom of bucket enters No. 1 mud cleaning bucket and washes mud; Primary brine is added in calcium-removing reactor, adds in the carbonization containing carbonate in calcium-removing reactor and water, in and the concentration numbers of water be 55-65tt, temperature is 35-40 degree, react 0.5 hour, obtains secondary distiller liquor; Secondary distiller liquor is put into secondary brine settling tank and clarifies 2-3 hour, obtained refined brine enters purified salt pond, and remaining secondary mud enters No. 2 mud cleaning buckets and washes mud.In method salt solution described in employing, calcium removal effect is better, but calcium magnesium can not be carried out simultaneously removing (magnesium ion content is greater than 6ppm, does not reach the salt of wormwood quality of production and requires), and dedoping step is cumbersome, affects working efficiency, too increases processing cost.
Chinese invention patent CN200910147104.4 discloses a kind of Repone K method of purification, it is for raw material with low levels Repone K, concrete operations are as follows: the sodium chloride-containing of low levels Repone K and normal temperature and the solution of Repone K at high temperature dissolve, be separated by press filtration, obtain the saturated clear liquid of high-temp chlorination potassium; Saturated for Repone K clear liquid being loaded can complete hermetic container, then-5 ~ 25 DEG C are cooled in sealed states, centrifugation is carried out after crystallize out, the crystal pure water obtained washs, then obtain by dehydrating the Repone K that purity reaches more than 99%, mother liquor returns above-mentioned steps and recycles.But this invention technology does not express the whereabouts of side product chlorinated sodium and calcium sulfate, method Repone K yield is simultaneously low, and (yield is only 42%, the too low production cost that causes of the utilization ratio of potassium is too high), it does not equally carefully state gained Potassium Chloride Product impurity index yet, and this technology does not obviously possess practical application meaning.
Chinese invention patent 201010569036.3 discloses one " brine rectification process of single stage method calcium-magnesium removing ", specifically describes as follows: first got from bittern tank by saturated bittern with pump, by heat exchanger, brine temperature is heated to 45-60 DEG C; Then the halogen after the first step preheating is made to enter reactor, in reactor, add sodium hydroxide and sodium carbonate, carry out refining reaction with after eliminating magnesium in bittern and calcium, the naoh concentration in bittern is 0.2-0.5 grams per liter, concentration of sodium carbonate is 0.3-0.5 grams per liter, and then gravity flow enters medial launder; With liquid feeding pump, the bittern after second step process is squeezed into HVMTM membrane filter again, filtering rear is 8.5-10.5 with salt acid for adjusting pH, then adds S-WAT and eliminates free chlorine, and crossing detection suspended solids SS amount is 0.1-0.2 mg/litre, from inflow refined brine tank, obtained primary brine.The design concept of traditional technology has been overturned in this invention, its theoretical foundation is, although magnesium hydroxide is colloid, to generate at itself and calcium carbonate, when jointly existing, due to co-precipitation simultaneously, magnesium hydroxide and calcium carbonate be combined with each other, particle increases, and its surface viscosity declines, and sticking power significantly reduces, can be removed by recoil on film surface, HVMTM membrane filter can not be affected and normally run; Simultaneously, the aperture of filtering membrane is 0.2-0.25 micron, under normal circumstances, refining reaction generate calcium carbonate granule in particle diameter be less than 0.2 micron account for 10%, in this technique, due to the existence of magnesium hydroxide, making to be combined with each other between calcium carbonate granule increases oarse-grained diameter, the amounts of particles being less than 0.2 micron is reduced further, thus improves filter effect.Therefore, completely unnecessaryly carry out complicated preprocessor, like this, the equipment relevant with pre-treatment such as iron trichloride venturi mixer pressure air-dissolving tank, material all can save.
Sylvite is a kind of mineral substance be present in various fruits, vegetables and beans, and it can prevent and treat hypertension.The blood pressure that the potassium existed in Cardia Salt inhibits sodium to bring out increases.The mankind are roughly the same with the absorption demand of sodium to potassium in meals, it is all the performance of potassium deficiency as the nervousness performance of muscle weakness, aggravation and irritability, mental disorientation, cardiomotility are irregular, many people, the particularly people of impoverished nation, due to enough fresh fruits and vegetables cannot be obtained, only have and meet their demand to potassium by other approach.The main component of salt is sodium-chlor, sodium-chlor is taken in too much can bring out hypertension again, cause the various diseases such as coronary heart disease, cerebral infarction, renal tubal dysfunction, retinopathy, have a strong impact on everybody quality of life even the life-span Cardia Salt that contains Repone K and sodium chloride mixture be balanced salt, it is suitable for suffering from hypertension and cardiopathic crowd.According to the concerned countries standard of edible salt, the sodium chloride content containing salt compounded of iodine has three ranks, one-level content >=99.1%, secondary >=98.5%, and three grades >=97%.Containing the sodium-chlor of 60% ~ 70% in Cardia Salt, also has the Repone K of 20% ~ 30% and the magnesium sulfate of 8% ~ 12% simultaneously.Cardia Salt, not only easily can reduce by the sodium of 30%, and the sodium in meals, potassium and magnesium three kinds of elements can also be helped to reach better balance, is conducive to preventing hypertension, protection cardiovascular and cerebrovascular.
The people such as Alves de Lima are entitled as on December 12nd, 2000 in No. 9806380Ath, the Brazilian patent of " Production of dietetic salt by mixing " (producing edible salt by hybrid system) and set forth, and produce by mixing sea salt, Repone K, Potassium Iodate and lagoriolite the low sodium edible salt being mixed with 4 parts of sodium-chlor and 6 parts of Repone K.The shortcoming of the method must obtain pure sodium-chlor and Repone K respectively, again its blending is obtained solid mixture, obviously be uneconomic for production cost, and solid and solid-phase mixing also uneven, the quality of product and uniform and stable property certainly will be affected.
Patent of invention CN2003080110956.7(PCT/IN2003/000449200312.31) provide a kind of preparation method of edible salt reclaiming Repone K simultaneously and be rich in KCl, the method comprises: (1) carries out desulfurization with calcium chloride to bittern; (2) bittern of desulfurization is evaporated; (3) desulfurization bittern is mixed with concentrated magnesium chloride solution obtain carnallitite again; (4) then use water decomposition carnallitite, obtain Repone K and remaining bittern; (5) concentrated remaining bittern, obtains the sodium-chlor as thick carnallitite and carnallite decomposition liquid in bittern and Repone K; (6) produce with the thick carnallitite of water decomposition the Cardia Salt and the carnallite decomposition liquid that are rich in Repone K; (7) collect carnallite decomposition liquid, with lime treatment, produce the filtrate of magnesium hydroxide and chloride containing calcium and Repone K; (8) by step 7) recycling in step 1), reclaim the Repone K be lost in carnallite decomposition liquid simultaneously; (9) the old halogen of recycling step 3), produces carnallitite and calcium chloride; (10) utilize excessive magnesium chloride to reclaim bromine and to obtain magnesium chloride.The Repone K that content is 98.5% can be produced by the method, simultaneously can the Cardia Salt of manufacture chloride containing potassium 45% and sodium-chlor 55%, it is high that this patent of invention technology has potassium resource utilization ratio, high-purity potassium chloride and chloride containing potassium Cardia Salt two kinds of products can be produced simultaneously, be suitable for the exploitation of large-scale sylvite ore.
A kind of method reclaiming Cardia Salt from bittern that patent of invention CN02827765.1 is fair, its concrete operations are as follows: (1) is being in the bittern of 29-30 degree Beaume containing 25-65 grams per liter vitriol, density, add the calcium chloride that concentration is 80-450 grams per liter, be used for processing vitriol in bittern, to generate insoluble calcium sulfate, in calcium chloride and bittern, the mol ratio of vitriol is 0.9-1.1:1; (2) separating calcium sulphate from depickling salt bittern, to obtain the bittern of calcium sulfate and desulfating; (3) evaporated by the bittern of the desulfating containing 90-135 grams per liter sodium-chlor and 20-25 grams per liter Repone K in salt pond, until its density reaches 30-33 degree Beaume, now too much salt is precipitated in salt pond to get off; (4) by shifting out the method for bittern gently, the too much salt described in being separated from concentrated bittern; (5) being evaporated further by bittern in second group of salt pond, is 3.5 degree Beaume to reach density, in salt pond, be now settled out the mixture of required sodium-chlor and carnallitite (Repone K and magnesium sulfate); (6) solid sediment scraped and pile up, and discharging mother liquor; (7) in stirred vessel, in the corresponding 1 part of solid sediment of 0.3-0.5 part water ratio stir process described in solid sediment, process after 20-60 minute and make Cardia Salt and a kind of liquid balanced each other with it; (8) by centrifugation, described solid is separated from liquid; (9) in carnallitite pond, the liquid recycle of magnesium chloride and 30-55 grams per liter sodium-chlor and Repone K will be dissolved with, to reclaim more sodium salt and sylvite; (10) known technology is adopted, dry Cardia Salt at 90-130 DEG C of temperature; (11) with the Potassium Iodate of 25-50ppm and the Magnesium Carbonate Light 41-45 of 0.01%-0.05% weight ratio, or in salt, residual magnesium chloride and sodium carbonate produce magnesiumcarbonate after reacting on the spot, process dried material, make it to have free-flowing property.
Summary of the invention
The method of high purity potassium chloride solution and coproduction Cardia Salt needed for the manufacture salt of wormwood that the technical problem to be solved in the present invention is to provide a kind of concise in technology; The industrial high purity potassium chloride solution adopting method of the present invention can obtain content (purity) to be greater than 99.0%.
In order to solve the problems of the technologies described above, the invention provides a kind of method of high purity potassium chloride solution and coproduction Cardia Salt needed for manufacture salt of wormwood, using agricultural grade Repone K as raw material, comprising the following steps:
1), Repone K dissolves rinsing:
In agricultural grade Repone K, add washing lotion under the mixing speed of 500 ~ 700 revs/min (being preferably 600 revs/min), in room temperature, stir rinsing 30 ~ 90min(be preferably 60min); Every 1000 kilograms of agricultural grade Repone K adapteds 750 ~ 850 liters of washing lotions (being preferably 800 liters);
Described washing lotion is purity (mass content) is the saturated solution of the Repone K of >=90% or following step 2) the Repone K rinsing liquid of gained (this Repone K rinsing liquid is capable of circulation reuse);
Described agricultural grade Repone K is purity (mass content) is the Repone K of 94.5 ~ 95.5%;
Remarks illustrate: time initial, be that the saturated solution of the Repone K of >=90% is as washing lotion by purity; Later all available step 2) the Repone K rinsing liquid of gained is as washing lotion;
2), centrifugal drip washing:
The gains of step 1) are carried out centrifugal (namely agricultural grade Repone K carries out centrifugal after the stirring rinsing of step 1)) in 1000 ~ 1200 revs/min; Carry out drip washing with the Repone K slag washing water of following step 4) gained or tap water in centrifugal process, the Repone K slag washing water of the step 4) gained needed for drip washing or tap water are 9 ~ 11L/100KG with the volume mass ratio of the agricultural grade Repone K in step 1); Obtain drip washing post chlorization potassium and Repone K rinsing liquid; Thus guarantee drip washing post chlorization potassium water content≤3.0% of centrifugal rear gained; Above-mentioned centrifugation time is about 8 ~ 12 minutes; Repone K purity (meter of giving money as a gift) >=99.0%;
Remarks illustrate: time initial, carry out drip washing with tap water; The Repone K slag washing water of all available following step 4) gained carries out drip washing later;
3), Repone K dissolves:
By step 2) to be dissolved in pH be that 9.4 ~ 9.6(is preferably 9.5 for the drip washing post chlorization potassium of gained) tap water or the Repone K slag washing water of following step 4) gained, obtain Klorvess Liquid I; The temperature controlling Klorvess Liquid I is 45 ~ 50 DEG C; Step 2) the drip washing post chlorization potassium of gained and pH be the tap water of 9.4 ~ 9.6 or the amount ratio of Repone K slag washing water be that 1g:2.8 ~ 3.2ml(is preferably 1g:3ml);
Described pH be 9.4 ~ 9.6 tap water be utilize potassium hydroxide to regulate the tap water of pH to 9.4 ~ 9.6;
Remarks illustrate: time initial, be dissolved in the tap water that pH is 9.4 ~ 9.6; All dissolve in the Repone K slag washing water of following step 4) gained later;
Utilize the waste heat that step 6) evaporates the steam condensate of Repone K rinsing liquid (filtrate namely described in step 6)) gained to carry out heating hydrotropy, thus the temperature realizing controlling Klorvess Liquid I is 45 ~ 50 DEG C;
4), removal of impurities, insulation precipitation, clear liquid filter:
First in Klorvess Liquid I, add cleaner, alkali and flocculating aids successively to stir, then at 45 ~ 50 DEG C, be incubated precipitation 1 ~ 3 hour (being preferably 2 hours), then filter operation (object is to remove suspension wherein, foreign material) is carried out, collect filtrate, described filtrate is Klorvess Liquid II; Filter cake tap water carries out pushing up washing or carrying out top with the waste water containing lower concentration Repone K produced when utilizing the high purity potassium chloride solution of step 5) gained to produce salt of wormwood to be washed, until the residual quantity≤3%(quality % of Repone K in rear filter cake is washed on top), the liquid produced during the filter wash cake of top is called Repone K slag washing water;
Remarks illustrate: push up the water yield of washing and be generally the tap water of every g filter cake adapted 5 ~ 10ml or the described waste water containing lower concentration Repone K; Push up the pressure washed and be about 0.6-0.7MPa;
Time initial, filter cake tap water carries out top and washes; Then, all available waste water containing lower concentration Repone K carries out top and washes;
Described cleaner is made up of calcium oxide, ammonium chloride and component A; Described component A is at least one in phosphoric acid, potassium primary phosphate and Secondary ammonium phosphate;
The consumption of calcium oxide is that 0.08 ~ 0.12%(of the drip washing post chlorization potassium quality used by step 3) is preferably 0.1%);
The consumption of ammonium chloride is 0.12% ~ 0.24% of the drip washing post chlorization potassium quality used by step 3);
The consumption of component A is 0.3% ~ 0.72% of the drip washing post chlorization potassium quality used by step 3);
Described alkali is potassium hydroxide, and add-on is that the pH adding the Klorvess Liquid after cleaner I is adjusted to 12 ± 0.2;
Described flocculating aids is at least one in wood shavings and flyash; Flocculating aids is that 1.5% ~ 2.5%(of drip washing post chlorization potassium quality used in step 3) is preferably 2%);
Remarks illustrate: Klorvess Liquid I, after above-mentioned stirring, insulation precipitation, filtration, can remove the impurity such as the vitriol in Klorvess Liquid I, calcium, magnesium, iron and heavy metal;
5), by the Repone K slag washing water allotment concentration of the Klorvess Liquid II of step 4) gained with step 4) gained, thus the Repone K in the Klorvess Liquid III of gained is made to be 250 ± 10g/L;
The Klorvess Liquid III of above-mentioned gained is detected, when meeting the following conditions simultaneously, becomes the high purity potassium chloride solution produced needed for salt of wormwood; Otherwise be back to step 4) and carry out removal of impurities, insulation precipitation, clear liquid filtration;
Containing Ca in Klorvess Liquid III
2+≤ 0.0001%, Mg
2+≤ 0.0001%, Fe≤0.0001%, heavy metal≤0.0001%, arsenic≤0.0001%, ss suspended solid≤0.5mg/L(remarks illustrate: all meet pH=12 ± 0.2 when meeting above-mentioned condition);
Remarks illustrate:
When Klorvess Liquid III cannot meet above-mentioned condition needs be back to step 4) time, that is, substitute the Klorvess Liquid I in former step 4) with Klorvess Liquid III, thus carry out removal of impurities, insulation precipitation, clear liquid filter;
Purity >=99.0% of the Repone K of gained after the drying of above-mentioned high purity potassium chloride solution, meets needed for salt of wormwood production.
6), step 2) the Repone K rinsing liquid of gained after≤10 times repeatedly use, for the preparation of Cardia Salt.
Remarks illustrate: content≤70% of sodium-chlor in Cardia Salt is such as 30 ~ 70%.
Improvement as the method for high purity potassium chloride solution needed for manufacture salt of wormwood of the present invention and coproduction Cardia Salt:
Described step 6) is: step 2) the Repone K rinsing liquid of gained after≤10 times repeatedly use, filter (object is removing visible foreign, makes filtrate reach clarity and requires); Gained filtrate carries out evaporation concentration, Repone K and the sodium-chlor poor solubility opposite sex is utilized to carry out separation and purification, respectively purity >=95% Repone K and the Cardia Salt of chloride containing potassium, the Repone K energy alternative steps 1 of described purity >=95%) in use as the agricultural grade Repone K of raw material.
Improvement as the method for high purity potassium chloride solution needed for manufacture salt of wormwood of the present invention and coproduction Cardia Salt: being filtered in described step 4) adopts air film type frame plate type pressure filter to carry out press filtration, and the aperture of filter cloth is 5 microns.
Further improvements in methods as high purity potassium chloride solution needed for manufacture salt of wormwood of the present invention and coproduction Cardia Salt:
The method utilizing the high purity potassium chloride solution of step 5) gained to produce salt of wormwood is ion exchange method; The steam condensed water waste heat containing lower concentration Repone K water reuse step 6) evaporation of filtrate (namely Repone K rinsing liquid filters the filtrate of gained) gained of gained carries out being heated to 45 ~ 50 DEG C; Thus to make in step 4) for pushing up the temperature of waste water containing lower concentration Repone K of washing to be 45 ~ 50 DEG C;
Step 4) top wash after filter cake as nitrogen-phosphorus-potassium compound fertilizer filler for agriculture production.
Remarks illustrate: the potassium chloride concentration in lower concentration Repone K waste water that contains of gained is about 2.5g/l, and the concentration of ammonium chloride is about 1.2g/l.
Further improvements in methods as high purity potassium chloride solution needed for manufacture salt of wormwood of the present invention and coproduction Cardia Salt:
Step 2) gained Repone K rinsing liquid can repeatedly use in step 1), and multiplicity is 1-10 time (be preferably 5-7 time, most preferably be 6 times).
Further improvements in methods as high purity potassium chloride solution needed for manufacture salt of wormwood of the present invention and coproduction Cardia Salt:
Described step 6) is:
Step 2) the Repone K rinsing liquid of gained through≤10 times after repeatedly (being such as 6 times) is reused, filter (object is removing visible foreign, makes filtrate reach clarity and requires); Gained filtrate is evaporation concentration at 120 ~ 125 DEG C, crystallisation by cooling is carried out in airtight container, obtained the mother liquor of Repone K and chloride containing potassium and sodium-chlor by centrifugation after crystallisation by cooling, purity >=95% of gained Repone K, can alternative steps 1) in use as the agricultural grade Repone K of raw material;
The mother liquor of described chloride containing potassium and sodium-chlor again passes through evaporation concentration at temperature is 130 ~ 135 DEG C, prepare the Cardia Salt (Large stone) of chloride containing potassium, after evaporation concentration, the mother liquor of gained recirculation can carry out evaporation concentration, thus make Repone K and sodium-chlor obtain 100% utilization, realize zero release.
Further improvements in methods as high purity potassium chloride solution needed for manufacture salt of wormwood of the present invention and coproduction Cardia Salt:
The steam condensate produced in evaporating concentration process described in step 6) and the waste heat of secondary steam, as the thermal source of the adjustment Klorvess Liquid I in step 3), and as the adjustment in step 4) for pushing up the thermal source of the waste water containing lower concentration Repone K washed.
In the present invention, room temperature refers to 10 ~ 25 DEG C.
In sum, the agricultural potassium chloride that the present invention is is about 95% by content is by the high purity potassium chloride needed for the salt of wormwood production that obtains content after the simple process such as dissolvings, rinsing, centrifugal and drip washing and be greater than 99.0%.
In the present invention:
1, Repone K rinsing liquid carries out the recycle of limited number of time, to reduce the processing cost of Repone K and to ensure the consistence of process post chlorization potassium quality.
2, Repone K rinsing liquid is by filter and evaporation concentration reclaims the Cardia Salt of Repone K without tramp material and chloride containing potassium.
3, the impurity such as the calcium in Klorvess Liquid, magnesium, iron and heavy metal are removed, to meet the specification of quality of method for producing potassium carbonate by ion exchange by the present invention completely.
4, make use of Repone K filter residue as N P and K multi-element compound fertilizer stopping composition.
5, when the Klorvess Liquid III of step 5) gained meets the following conditions, the high purity potassium chloride solution that can be directly used in method for producing potassium carbonate by ion exchange is just become:
Ca
2+≤ 0.0001%, Mg
2+≤ 0.0001%, Fe≤0.0001%, heavy metal≤0.0001%, arsenic≤0.0001%, ss suspended solid≤0.5mg/L;
Its advantage is: Microamounts of Hydrogen potassium oxide contained in Klorvess Liquid effectively can be utilized like this by complete for the oil soluble bicarbonate of ammonia anti-hard caking agent cleaning remained in ion exchange resin, can significantly improve the switching performance of resin and the quality of salt of wormwood.
In a word, the present invention can be by content the agriculture grade potassium chloride of about 95% by steps such as rinsing, dissolving, removal of impurities, sedimentation and filtrations, prepare and produce the high purity potassium chloride solution of salt of wormwood, wherein containing Ca
2+≤ 0.0001%, Mg
2+≤ 0.0001%, Fe≤0.0001%, ss suspended solid≤0.1mg/L, pH=12 ± 0.2, more than KCE content>=99.0%, meets the quality standard of method for producing potassium carbonate by ion exchange completely.Also Repone K rinsing liquid and leacheate can be used by recirculation simultaneously, and then pass through evaporation concentration, dissolution characteristics according to Repone K and sodium-chlor carries out Crystallization Separation, reclaim gained Repone K to reuse as raw material, the mixture of gained chloride containing potassium and sodium-chlor meets Cardia Salt specification of quality.The present invention adopts single stage method removal of impurities, can significantly reduce removal of impurities cost, enhance productivity, and reduces facility investment.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is for producing the process flow sheet of the method for high purity potassium chloride solution and coproduction Cardia Salt needed for salt of wormwood.
Embodiment
A kind of method of high purity potassium chloride solution and coproduction Cardia Salt needed for embodiment 1, manufacture salt of wormwood, as raw material, carry out following steps using agricultural grade Repone K (purity is the Repone K of 95.1%) successively:
1), Repone K dissolves rinsing:
Be in the agricultural grade Repone K input 2400L washing lotion of 95.1% by 3000Kg content (purity), at room temperature stir rinsing 60min with the rotating speed of 600 revs/min.
Washing lotion is purity is the saturated solution of the Repone K of >=90% or following step 2) the Repone K rinsing liquid (being cycled to repeat use) of gained.
Remarks illustrate: time initial, use above-mentioned purity to be the saturated solution of the Repone K of >=90%; Then, all following step 2 can be used) centrifugal gained Repone K rinsing liquid (for better within reusing 6 times).
2), centrifugal drip washing:
By gains (namely stirring the agricultural grade Repone K after rinsing through the step 1)) centrifuge dripping (carry out drip washing with the Repone K slag washing water of the following step 4) gained of 300L in centrifugal process or carry out drip washing with the tap water of 300L) of step 1), obtain drip washing post chlorization potassium and Repone K rinsing liquid.
Centrifugal rotational speed controls at 1000-1200 rev/min, and centrifugation time is 10 minutes.
Remarks illustrate 1: time initial, carry out drip washing with tap water; The Repone K slag washing water of all available following step 4) gained carries out drip washing later;
Remarks illustrate 2: drip washing post chlorization potassium is used for next step and dissolves, and the rinsing process that Repone K rinsing liquid returns step 1) can repeat recycling.
Part moisture content is taken away due to potassium can be chlorinated in rinse cycle, thus quantity not sufficient when causing Repone K rinsing liquid to be used by recirculation as washing lotion in step 1), the available saturated potassium chloride solution of the not enough part (purity is the saturated solution of the Repone K of >=90%) in therefore using is supplemented in Repone K rinsing liquid as washing lotion; Thus guarantee that the amount ratio of Repone K and washing lotion is 1000kg:800L, i.e. 1000 kilograms of raw material Repone K: 800 liters of washing lotions, it is 10 times that the present embodiment repeats secondary, the concrete data of each gained Repone K mass analysis are as described in Table 1, and rinsing liquid reuses 6 times can ensure above-mentioned steps 2) the drip washing post chlorization potassium content of gained is greater than 99.0%.
Table 1, Repone K mass analysis correlation data
| Recycling Mother Solution number of times | Repone K, % | Calcium, % | Magnesium, % | Sulfate radical, % | Water content, % |
| Raw material Repone K | 95.1 | 0.283 | 0.082 | 0.22 | 0.43 |
| 0 | 99.4 | 0.031 | 0.016 | 0.028 | 2.78 |
| 1 | 99.3 | 0.042 | 0.022 | 0.042 | 2.71 |
| 2 | 99.3 | 0.063 | 0.030 | 0.050 | 2.74 |
| 3 | 99.2 | 0.078 | 0.033 | 0.061 | 2.89 |
| 4 | 99.2 | 0.086 | 0.041 | 0.068 | 2.91 |
| 5 | 99.1 | 0.091 | 0.046 | 0.071 | 2.87 |
| 6 | 99.0 | 0.098 | 0.049 | 0.074 | 2.88 |
| 7 | 98.6 | 0.112 | 0.051 | 0.076 | 2.79 |
| 8 | 97.8 | 0.121 | 0.051 | 0.078 | 2.98 |
| 9 | 97.2 | 0.128 | 0.053 | 0.078 | 2.85 |
| 10 | 96.3 | 0.137 | 0.053 | 0.081 | 2.97 |
3), Repone K dissolves:
By 5000kg step 2) the drip washing post chlorization potassium of the gained pH that is dissolved in 15 cubic metres is Repone K slag washing water (the wherein chloride containing potassium 12g/L of the tap water (utilizing potassium hydroxide to regulate pH to be 9.5) of 9.5 or the following step 4) gained of 15 cubic metres, pH is 9.5) in, the exhaust-heat heating to 50 DEG C of the steam condensate utilizing following step 6) to produce, obtains Klorvess Liquid I;
Remarks illustrate: time initial, be dissolved in the tap water that pH is 9.5; All dissolve in the Repone K slag washing water of step 4) gained later;
4), removal of impurities, insulation precipitation, clear liquid filter:
5Kg calcium oxide is added in Klorvess Liquid I, stir after 10min adds 50L potassium primary phosphate mother liquor (concentration is 300g/L) and 6Kg ammonium chloride again and stir 10min, add potassium hydroxide (about 50Kg) afterwards in order to regulator solution pH, control pH value of solution=12 ± 0.2, finally add 100Kg sawdust, stir 30min; Insulation nature precipitation is carried out 2 hours under about 45 ~ 50 DEG C conditions;
Then, press filtration (pressure is 0.6-0.7MPa) is carried out by air film type frame plate type pressure filter; The aperture of filter cloth is 5 microns (can retain the impurity that particle diameter is more than 5 microns), respectively must as the Klorvess Liquid II of filtrate and filter cake;
Filter cake tap water carries out pushing up washing or carrying out top with the waste water containing lower concentration Repone K produced when utilizing the high purity potassium chloride solution of step 5) gained to produce salt of wormwood to be washed, until residual quantity≤3% of Repone K in rear filter cake is washed on top, the liquid that top filter wash cake (Repone K filter cake) produces is called Repone K slag washing water;
Remarks illustrate: time initial, filter cake tap water carries out top and washes; Then, all available waste water containing lower concentration Repone K carries out top and washes;
Be specially:
Ion exchange method is adopted to utilize high purity potassium chloride solution (following step 5) gained) to produce salt of wormwood, what produced is heated to 45 ~ 50 DEG C containing the heat produced in the following step 6) evaporating concentration process of water reuse of lower concentration Repone K, utilizes the waste water containing lower concentration Repone K after above-mentioned heating to carry out top to filter cake and washes (pressure is about 0.6-0.7MPa); The top time of washing is about 30-60 minute, thus guarantees to push up residual quantity≤3% washing Repone K in rear filter cake; Use the pressurized air top blast of 0.8-1.2MPa pressure after closing water valve again, make Repone K cake moisture be less than 50%, dry after filter residue is unloaded.Repone K filter residue after drying is through assay, wherein contain potassium 3.2%, phosphorus 15.6%, nitrogen 5.3%, magnesium 8.9%, calcium 16.1%, iron 0.32%, heavy metal (in Pb) < 0.01%(Repone K filter residue analytical data all in butt), it can be used as the filler of nitrogen-phosphorus-potassium compound fertilizer.
5), by the Repone K slag washing water allotment concentration of the Klorvess Liquid II of step 4) gained with step 4) gained, thus the Repone K in the Klorvess Liquid III of gained is made to be 253g/L;
After testing: in Klorvess Liquid III, Repone K purity is 99.1%, and potassium chloride concentration 253g/L, containing Ca
2+≤ 0.0001%, Mg
2+≤ 0.0001%, Fe≤0.00005%, heavy metal≤0.00005%, arsenic≤0.0001%, ss suspended solid is 0.03mg/L; PH=12, meets the specification of quality of method for producing potassium carbonate by ion exchange.
Therefore, this Klorvess Liquid III is for producing the high purity potassium chloride solution needed for salt of wormwood.
6), following 2 kinds of schemes are divided into:
Scheme 1:
By embodiment 1 step 2) centrifugal gained reuses the Repone K rinsing liquid after 6 times, first filters with plate and frame(type)filter press that (pressure is 0.6-0.7MPa; The impurity that particle diameter is 5 microns can be retained) to remove suspended substance wherein;
The filtrate (i.e. above-mentioned Repone K rinsing liquid clear liquor after filtering) of gained carries out evaporation concentration at 120 ~ 125 DEG C, and when 3000L Repone K rinsing liquid is evaporated to remaining 2200L, the concentrated solution of gained moves into natural cooling crystallization in airtight crystallizer;
After being down to room temperature Deng concentrated solution temperature, in the chuck of crystallizer, passing into refrigerated brine, concentrated solution temperature is down to less than 5 DEG C; Be separated by centrifugal (1200 revs/min), obtain 220Kg Repone K (KCE content is 95.5%), it can be used as step 1) raw material Repone K to use (that is, substituting agricultural grade Repone K);
In the 2100L mother liquor of centrifugation gained, add 55 kilograms, sodium carbonate, natural sedimentation after stirring and dissolving, filter to isolate supernatant liquid as the stock liquid producing Cardia Salt;
Supernatant liquid Returning evaporimeter evaporation concentration again, vaporization temperature is 130-135 DEG C, when having a large amount of sodium chloride crystal to separate out in device to be evaporated, when continuation evaporation concentration to volume is 1000L, centrifugal (1200 revs/min) are separated while hot, obtaining sodium-chlor 180Kg(sodium chloride content is 98.3%, Repone K 1.2%);
Secondary concentration mother liquor after centrifugal removing sodium chloride crystal is moved into crystallization water cooler, carry out Temperature fall, equitemperature drops to room temperature, centrifugal (1200 revs/min) are separated, and obtain Cardia Salt (wherein chloride containing potassium 54.6%, the sodium-chlor 42.8% of 350Kg chloride containing potassium, magnesium chloride 1.2%, calcium chloride 0.6%), the crystallization of centrifugal mother liquid obtained repeated evaporation again, to reclaim the Cardia Salt of chloride containing potassium.
Scheme 2:
By embodiment 1 step 2) centrifugal gained reuses the Repone K rinsing liquid after 6 times, first filters with plate and frame(type)filter press that (pressure is 0.6-0.7MPa; The impurity that particle diameter is 5 microns can be retained) to remove suspended substance wherein;
The filtrate (i.e. above-mentioned Repone K rinsing liquid clear liquor after filtering) of gained carries out evaporation concentration at 120-125 DEG C, and when 3000L rinsing liquid is evaporated to remaining 2200L, concentrated solution moves into natural cooling crystallization in airtight crystallization;
After being down to room temperature Deng concentrated solution temperature, in the chuck of crystallizer, passing into refrigerated brine, cool the temperature to less than 5 DEG C; By centrifugation (1200 revs/min), obtain 220Kg Repone K (KCE content is 95.5%), it can be used as raw material Repone K to use (that is, substituting agricultural grade Repone K);
Add 55 kilograms, sodium carbonate in the 2100L mother liquor of centrifugation gained, natural sedimentation after stirring and dissolving, the supernatant liquid filtered to isolate is as the stock liquid producing Cardia Salt;
Supernatant liquid returns steaming device evaporation concentration again, vaporization temperature is 130-135 DEG C, when having a large amount of sodium chloride crystal to separate out in device hair device, continuing evaporation concentration to volume is 1000L, and secondary concentration liquid moves into crystallization water cooler Temperature fall to room temperature, centrifugation, obtain Cardia Salt (chloride containing potassium 32.6%, sodium-chlor 62.4%, the magnesium chloride 1.2% of 530Kg chloride containing potassium, calcium chloride 0.6%), mother liquor repeats the Cardia Salt that above step reclaims chloride containing potassium again.
Illustrated by such scheme 1 and scheme 2: the Cardia Salt meeting different user requirement can be produced by technique adjustment.
A kind of method of high purity potassium chloride solution and coproduction Cardia Salt needed for embodiment 2, manufacture salt of wormwood, as raw material, carry out following steps using agricultural grade Repone K (purity is the Repone K of 95.1%) successively:
Step 1) ~ step 3) is with embodiment 1.
4), removal of impurities, insulation precipitation, clear liquid filter:
5Kg calcium oxide is added in Klorvess Liquid I, stir after 10min adds 80L potassium primary phosphate mother liquor (concentration is 300g/L) and 8Kg ammonium chloride again and stir 10min, add potassium hydroxide afterwards in order to regulator solution pH, control pH value of solution=12 ± 0.2, finally add 100Kg sawdust, stir 30min; Insulation nature precipitation is carried out 2 hours under about 45-50 DEG C condition;
All the other are with the step 4) of embodiment 1.
Repone K filter residue after drying is through assay, wherein contain potassium 3.0%, phosphorus 17.8%, nitrogen 5.9%, magnesium 8.9%, calcium 17.8%, iron 0.30%, heavy metal (in Pb) < 0.01%(Repone K filter residue analytical data all in butt), it can be used as the filler of nitrogen-phosphorus-potassium compound fertilizer.
5), by the Repone K slag washing water allotment concentration of the Klorvess Liquid II of step 4) gained with step 4) gained, thus the Repone K in the Klorvess Liquid III of gained is made to be 253g/L;
The Klorvess Liquid III of gained meets the following conditions: Repone K purity>=99.1%, containing Ca
2+: 0, Mg
2+: 0, Fe≤0.00005%, heavy metal≤0.00005%, arsenic≤0.0001%, ss suspended solid is 0.02mg/L; PH=12, meets the specification of quality of method for producing potassium carbonate by ion exchange.
Therefore, this Klorvess Liquid III is for producing the high purity potassium chloride solution needed for salt of wormwood.
Step 6) can refer to embodiment 1.
A kind of method of high purity potassium chloride solution and coproduction Cardia Salt needed for embodiment 3, manufacture salt of wormwood, as raw material, carry out following steps using agricultural grade Repone K (purity is the Repone K of 95.1%) successively:
Step 1) ~ step 3) is with embodiment 1.
4), removal of impurities, insulation precipitation, clear liquid filter:
5Kg calcium oxide is added in Klorvess Liquid I, stir after 10min adds 120L potassium primary phosphate mother liquor (concentration is 300g/L) and 12Kg ammonium chloride again and stir 10min, add potassium hydroxide afterwards in order to regulator solution pH, control pH value of solution=12 ± 0.2, finally add 100Kg sawdust, stir 30min; Insulation nature precipitation is carried out 2 hours under about 45-50 DEG C condition.
All the other are with the step 4) of embodiment 1.
Repone K filter residue after drying is through assay, wherein contain potassium 3.1%, phosphorus 18.7%, nitrogen 6.2%, magnesium 8.9%, calcium 17.6%, iron 0.34%, heavy metal (in Pb) < 0.01%(Repone K filter residue analytical data all in butt), it can be used as the filler of nitrogen-phosphorus-potassium compound fertilizer.
5), by the Repone K slag washing water allotment concentration of the Klorvess Liquid II of step 4) gained with step 4) gained, thus the Repone K in the Klorvess Liquid III of gained is made to be 252g/L;
The Klorvess Liquid III of gained meets the following conditions: Repone K purity>=99.1%, potassium chloride concentration 252g/L, Ca
2+: 0, Mg
2+: 0, Fe≤0.00005%, heavy metal≤0.00005%, ss suspended solid is 0.02mg/L, pH=12, meets the specification of quality of method for producing potassium carbonate by ion exchange.
Therefore, this Klorvess Liquid III is for producing the high purity potassium chloride solution needed for salt of wormwood.
Step 6) can refer to embodiment 1.
Comparative example:
Comparative example 1: be the agricultural grade Repone K of 95% according to the open described a kind of Repone K method of purification process content of Chinese invention patent CN200910147104.4.By 1000Kg content be 95.1% raw material Repone K drop into the sodium-chlor of 3000L normal temperature and Repone K altogether in saturated solution, at high temperature stirring and dissolving, is heated to boiling, then is separated by press filtration, obtains the saturated clear liquid of 2500L high-temp chlorination potassium; Saturated for high-temp chlorination potassium clear liquid being loaded can complete hermetic container, then 10 DEG C are cooled in sealed states, centrifugation is carried out after crystallize out, obtain 550Kg solid, with the drip washing of 50Kg pure water, obtain 531Kg Repone K by dehydrating, KCE content is 98.3%, do not reach the specification of quality produced salt of wormwood and need, mother liquor returns above-mentioned steps and carries out recirculation utilization.Contrast experiment finds, the open described a kind of Repone K method of purification of Chinese invention patent CN200910147104.4, on the one hand because high temperature filtration gained sodium-chlor is containing a large amount of calcium sulfate and Repone K, cannot recycle, lead Repone K raw material availability lower, need to consume a large amount of steam, processing cost is uneconomical.Through repeatedly cyclical operation, sodium-chlor and Repone K are total to saturated mother liquor amount and get more and more and cannot dispose, and this technology does not obviously possess practical application meaning as method for producing potassium carbonate by ion exchange raw material Repone K pre-treatment aspect.
Comparative example 2: the impurity in the method process Klorvess Liquid of a kind of refined brine provided according to Chinese invention patent CN200410012535.7, the method for a kind of refined brine adopting Chinese invention patent CN200410012535.7 to provide specifically removes calcium in Klorvess Liquid, magnesium ion obtains refined potassium chloride.Repone K after 1000kg rinsing is dissolved in 3 cubic metres of Repone K filter residue rinse water (wherein chloride containing potassium 12g/L, pH=9.5), obtains Klorvess Liquid I; In Klorvess Liquid I, add the 20 liters of milk of limes and 5 liters of settling agent PAM that prepare, stirring reaction 0.5 hour obtained distiller liquor, natural subsidence 1 hour, obtains 3.5 cubic metres of Klorvess Liquids II of clarification; In 3.5 cubic metres of Klorvess Liquids II, add carbonated titre is in the carbonization of 60tt and 200 liters, water, and stir static after 30 minutes, carry out press filtration after 3 hours by frame plate type pressure filter, filtrate chloride containing potassium is 256g/L, Ca
2+: 0.0062%, Mg
2+: 0.0048%, ss suspended solid is 1.52mg/L, pH=6.6, does not reach the specification of quality of method for producing potassium carbonate by ion exchange to Klorvess Liquid, and operates cumbersome.
Comparative example 3: disclose one " brine rectification process of single stage method calcium-magnesium removing " according to Chinese invention patent 201010569036.3 and process impurity in Klorvess Liquid, concrete operations are as follows: first dissolved by the Repone K after rinsing process, by heat exchanger, Klorvess Liquid is heated to 45-60 DEG C; Klorvess Liquid after preheating is entered reactor, sodium hydroxide and sodium carbonate is added in reactor, carry out refining reaction to eliminate magnesium in Klorvess Liquid and calcium, the naoh concentration controlled in Klorvess Liquid is 0.2-0.5 grams per liter, concentration of sodium carbonate is 0.3-0.5 grams per liter, and then gravity flow enters medial launder; With liquid feeding pump, pretreated for reaction Klorvess Liquid is squeezed into HVMTM membrane filter again, filter to obtain refined potassium chloride solution.Gained refined potassium chloride solution chloride containing potassium 250g/L, Ca
2+: 0.0028%, Mg
2+: 0.0016%, Fe:0.0005%, heavy metal: 0.001%, ss suspended solid is 1.2mg/L, pH=10.6, although simplify to some extent than the technique of traditional refined brine, but do not reach the specification of quality of method for producing potassium carbonate by ion exchange to Klorvess Liquid, particularly it adds a large amount of sodium hydroxide and sodium carbonate in dedoping step, cause in institute's Klorvess Liquid sodium-chlor containing too high, cause salt of wormwood content on the low side.。
Comparative example 4:
Change in the step 1) of embodiment 1, the volume (specifically as shown in table 1) of the washing lotion of every 1000 kilograms of agricultural grade Repone K institute adapteds, all the other content and steps 2 of step 1)) be equal to embodiment 1.
The content of the drip washing post chlorization potassium of gained is as shown in table 2 (Recycling Mother Solution number of times is 0 time).
Table 2
| Sequence number | Repone K amount (kilogram) | Rinsing liquid measure (L) | Process post chlorization potassium content (%) |
| 1 | 1000 | 500 | 98.2 |
| 2 | 1000 | 600 | 98.6 |
| 3 | 1000 | 700 | 99.1 |
| 4 | 1000 | 800 | 99.4 |
| 5 | 1000 | 900 | 99.4 |
| 6 | 1000 | 1000 | 99.4 |
| 7 | 1000 | 1100 | 99.5 |
| 8 | 1000 | 1200 | 99.5 |
As can be seen from this comparative test result, the ratio of raw material Repone K and rinsing liquid has a great impact wash effect, but after reaching certain proportion, treatment effect increases not obvious, but production efficiency declines a lot; Rinsing liquid additional proportion is too low, just very large on treatment effect impact, when the rinsing liquid that 1000 kilograms of raw material Repone K add is less than 700L, KCE content after process does not reach specification of quality, KCE content is less than 99%, therefore, needs strict to control raw material Repone K and the suitable ratio of rinsing liquid just can reach satisfied treatment effect, consider achievement and treatment effect, every 1000 kilograms of agricultural grade Repone K adapteds 800 liters of washing lotion the bests.
Comparative example 5:
Change rotating speed and the time (specifically as shown in table 3) of the stirring rinsing in the step 1) of embodiment 1; All the other content and steps 2 of step 1)) be equal to embodiment 1.
The content of the drip washing post chlorization potassium of gained is as shown in table 3 (Recycling Mother Solution number of times is 0 time).
Table 3
| Time (min) | Rotating speed (rev/min) | Rinsing post chlorization potassium content (%) |
| 30 | 600 | 98.8 |
| 45 | 600 | 99.1 |
| 60 | 600 | 99.4 |
| 75 | 600 | 99.4 |
| 90 | 600 | 99.4 |
| 60 | 500 | 99.2 |
| 60 | 550 | 99.3 |
| 60 | 600 | 99.4 |
| 60 | 650 | 99.4 |
| 60 | 700 | 99.4 |
Churning time can affect wash effect, and when churning time is less than 60 minutes, wash effect improves along with time lengthening; But after churning time reaches 60 minutes, then time expand wash effect is not affected; Mixing speed also can affect wash effect, but affects after rotating speed reaches 600 revs/min, improves rotating speed and also can not improve wash effect again.
Comparative example 6:
Change kind and the weight (specifically as shown in table 4) of cleaner used in embodiment 1 step 4), all the other are equal to the step 4) of embodiment 1;
Step 1) ~ step 3) and step 5) are equal to embodiment 1.
The foreign matter content of the Klorvess Liquid III of gained is as shown in table 4 (potassium primary phosphate mother liquid concentration is 300g/L).
Table 4
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (7)
1. the method for high purity potassium chloride solution and coproduction Cardia Salt needed for manufacture salt of wormwood, using agricultural grade Repone K as raw material, is characterized in that comprising the following steps:
1), Repone K dissolves rinsing:
In agricultural grade Repone K, add washing lotion in room temperature, stir rinsing 30 ~ 90min under the mixing speed of 500 ~ 700 revs/min; Every 1000 kilograms of agricultural grade Repone K adapteds 750 ~ 850 liters of washing lotions;
Described washing lotion is purity is the saturated solution of the Repone K of >=90% or following step 2) the Repone K rinsing liquid of gained;
Described agricultural grade Repone K to be purity be 94.5 ~ 95.5% Repone K;
2), centrifugal drip washing:
By step 1) gains carry out centrifugal in 1000 ~ 1200 revs/min; By step 4 in centrifugal process) the Repone K slag washing water of gained or tap water carry out drip washing, the following step 4 needed for drip washing) the Repone K slag washing water of gained or tap water and step 1) and in the volume mass ratio of agricultural grade Repone K be 9 ~ 11L/100Kg; Obtain drip washing post chlorization potassium and Repone K rinsing liquid;
Described drip washing post chlorization potassium water content≤3.0%;
3), Repone K dissolves:
By step 2) to be dissolved in pH be the tap water of 9.4 ~ 9.6 or following step 4 for the drip washing post chlorization potassium of gained) the Repone K slag washing water of gained, obtain Klorvess Liquid I; The temperature controlling Klorvess Liquid I is 45 ~ 50 DEG C; Step 2) the drip washing post chlorization potassium of gained and pH be the tap water of 9.4 ~ 9.6 or the amount ratio of Repone K slag washing water be 1g:2.8 ~ 3.2ml;
Described pH be 9.4 ~ 9.6 tap water be utilize potassium hydroxide to regulate the tap water of pH to 9.4 ~ 9.6;
4), removal of impurities, insulation precipitation, clear liquid filter:
First in Klorvess Liquid I, add cleaner, alkali and flocculating aids successively to stir, then at 45 ~ 50 DEG C, be incubated precipitation 1 ~ 3 hour, then carry out filter operation, collect filtrate, described filtrate is Klorvess Liquid II; Filter cake tap water carry out top wash or with utilizing step 5) waste water containing lower concentration Repone K that produces when producing salt of wormwood of the high purity potassium chloride solution of gained carries out top and washes, until residual quantity≤3% of Repone K in rear filter cake is washed on top, the liquid produced during the filter wash cake of top is called Repone K slag washing water;
Described cleaner is made up of calcium oxide, ammonium chloride and component A; Described component A is at least one in phosphoric acid, potassium primary phosphate and Secondary ammonium phosphate;
The consumption of calcium oxide is step 3) in used drip washing post chlorization potassium quality 0.08 ~ 0.12%;
The consumption of ammonium chloride is step 3) in used drip washing post chlorization potassium quality 0.12% ~ 0.24%;
The consumption of component A is step 3) in used drip washing post chlorization potassium quality 0.3% ~ 0.72%;
Described alkali is potassium hydroxide, and add-on is that the pH adding the Klorvess Liquid after cleaner I is adjusted to 12 ± 0.2;
Described flocculating aids is at least one in wood shavings and flyash; Flocculating aids is step 3) in used drip washing post chlorization potassium quality 1.5% ~ 2.5%;
5), by step 4) Klorvess Liquid II step 4 of gained) the Repone K slag washing water allotment concentration of gained, thus make the Repone K in the Klorvess Liquid III of gained be 250 ± 10g/L;
The Klorvess Liquid III of above-mentioned gained is detected, when meeting the following conditions simultaneously, becomes the high purity potassium chloride solution produced needed for salt of wormwood; Otherwise be back to step 4) carry out removal of impurities, insulation precipitation, clear liquid filtration;
Containing Ca in Klorvess Liquid III
2+≤ 0.0001%, Mg
2+≤ 0.0001%, Fe≤0.0001%, heavy metal≤0.0001%, arsenic≤0.0001%, ss suspended solid≤0.5mg/L;
6), step 2) the Repone K rinsing liquid of gained after≤10 times repeatedly use, for the preparation of Cardia Salt.
2. the method for high purity potassium chloride solution and coproduction Cardia Salt needed for manufacture salt of wormwood according to claim 1, is characterized in that:
Described step 6) be: step 2) the Repone K rinsing liquid of gained after≤10 times repeatedly use, filter; Gained filtrate carries out evaporation concentration, Repone K and the sodium-chlor poor solubility opposite sex is utilized to carry out separation and purification, respectively purity >=95% Repone K and the Cardia Salt of chloride containing potassium, the Repone K energy alternative steps 1 of described purity >=95%) in use as the agricultural grade Repone K of raw material.
3. the method for high purity potassium chloride solution and coproduction Cardia Salt needed for manufacture salt of wormwood according to claim 2, is characterized in that: described step 4) in be filtered into and adopt air film type frame plate type pressure filter to carry out press filtration, the aperture of filter cloth is 5 microns.
4. the method for high purity potassium chloride solution and coproduction Cardia Salt needed for manufacture salt of wormwood according to claim 3, is characterized in that:
Utilizing step 5) the high purity potassium chloride solution of the gained method of producing salt of wormwood is ion exchange method; Gained containing lower concentration Repone K water reuse step 6) steam condensed water waste heat of evaporation of filtrate gained carries out being heated to 45 ~ 50 DEG C; Thus make step 4) in be 45 ~ 50 DEG C for pushing up the temperature of waste water containing lower concentration Repone K of washing;
Step 4) push up the filter cake after washing as nitrogen-phosphorus-potassium compound fertilizer filler for agriculture production.
5. the method for high purity potassium chloride solution and coproduction Cardia Salt needed for manufacture salt of wormwood according to claim 4, is characterized in that:
Step 2) gained Repone K rinsing liquid is in step 1) in can repeatedly use, multiplicity is 1-10 time.
6. the method for high purity potassium chloride solution and coproduction Cardia Salt needed for manufacture salt of wormwood according to claim 5, is characterized in that:
Described step 6) be:
Step 2) the Repone K rinsing liquid of gained after repeatedly using, filter; Gained filtrate is evaporation concentration at 120 ~ 125 DEG C, crystallisation by cooling is carried out in airtight container, obtained the mother liquor of Repone K and chloride containing potassium and sodium-chlor by centrifugation after crystallisation by cooling, purity >=95% of gained Repone K, can alternative steps 1) in use as the agricultural grade Repone K of raw material;
The mother liquor of described chloride containing potassium and sodium-chlor again passes through evaporation concentration at temperature is 130 ~ 135 DEG C, prepare the Cardia Salt of chloride containing potassium, after evaporation concentration, the mother liquor of gained recirculation can carry out evaporation concentration, thus makes Repone K and sodium-chlor obtain 100% utilization, realizes zero release.
7. the method for high purity potassium chloride solution and coproduction Cardia Salt needed for manufacture salt of wormwood according to claim 6, it is characterized in that: step 6) described in evaporating concentration process in the waste heat of the steam condensate that produces and secondary steam, as step 3) in the thermal source of adjustment Klorvess Liquid I, and as step 4) in adjustment for pushing up the thermal source of the waste water containing lower concentration Repone K washed.
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| CN104192866B (en) * | 2014-08-25 | 2016-04-13 | 连云港树人科创食品添加剂有限公司 | A kind of method removing ammonium in Repone K |
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