CN103466662B - Method for preparing potassium sulfate with large grain diameter by utilizing reaction crystallization - Google Patents
Method for preparing potassium sulfate with large grain diameter by utilizing reaction crystallization Download PDFInfo
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- CN103466662B CN103466662B CN201310436468.0A CN201310436468A CN103466662B CN 103466662 B CN103466662 B CN 103466662B CN 201310436468 A CN201310436468 A CN 201310436468A CN 103466662 B CN103466662 B CN 103466662B
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Abstract
The invention relates to a method for preparing potassium sulfate with a large grain diameter by utilizing reaction crystallization. The method comprises the following processes of two aspects: carrying out double decomposition on picromerite and potassium chloride to prepare the potassium sulfate, and growing potassium sulfate crystal in a solution. According to the invention, the balanced mother solution of potassium sulfate is taken as a substrate, when the mixed slurry of the picromerite and the potassium chloride is gradually added to the mother solution, the mixed slurry and the mother solution are reacted to generate the potassium sulfate and form a supersaturated solution, and pushing force is generated so that the potassium sulfate crystal grows; meanwhile, the supersaturation degree of the solution is controlled by controlling charging rate, so that the nucleation rate is prevented from being excessively fast, and the crystal size is prevented from being excessively fine. The obtained product, namely the potassium sulfate crystal, can achieve the average grain diameter more than 250 micrometers, achieve the K2O contained in the potassium sulfate more than 51% and meet the requirement for premium-grade standard of the potassium sulfate used for agriculture in a water-salt system process. The method disclosed by the invention has the advantages of abundance and easiness for obtaining of raw materials, simple process and recycling of the raw materials and greatly reduces the production cost of the potassium sulfate.
Description
Technical field
Technical scheme of the present invention belongs to the preparation of potassium sulfate, specifically, is a kind of method that schoenite and Repone K prepare Large stone potassium sulfate.
Background technology
Potassium sulfate is a kind of chlorideless potassic fertilizer of high-quality, the high (K of its effective constituent
2o ~ 50%), salt index is low, water absorbability is little, be widely used in tobacco, sugarcane, tea tree, mulberry tree, potato, citrus, watermelon etc. and avoid in the cash crop of chlorine.The main production process of potassium sulfate has sulfuric acid process, double decomposition, seawater or bittern to extract potassium sulfate, solid kalium mine extraction method etc., but its product is all the flour that size is less, particle diameter is generally below 90 μm, in preparation process, easily there is dust, and be easy to when using between agriculture to cause the loss of potassium sulfate and soil nutrient unbalanced.Along with Chinese Agricultural Mechanization degree improves, seeding and fertilizing is at a loss as to what to do especially to powdered fertilizer, and therefore, the demand of market to Large stone potassium sulfate is increasing.
At present, the production of large-particle potassium sulfate makes granular potassium sulfate become large mainly through adding stiffening agent, coating-forming agent and tensio-active agent etc.CN85103968 discloses a kind of method utilizing tensio-active agent potassium sulfate to be suppressed granulating, be by a small amount of water being dissolved in containing tensio-active agent or being scattered in wherein is mixed with powdered potassium sulfate, then make mixture suppress granulating and obtain granular potassium sulfate.CN87105366 discloses a kind of method of wet granulation; being be added to by being selected from least one component in a group of calcium hydroxide, calcium oxide, calcium carbonate, magnesium hydroxide, magnesium oxide, magnesiumcarbonate and ammonia transforming in potassium sulfate and contained unconverted sulfuric acid of being obtained by reacting in anhydrous state by Repone K and sulfuric acid, obtaining succeeded by wet granulation.These method energy consumptions are high, and loss is large, and workshop dust pollution is serious.Therefore, directly go out Large stone potassium sulfate from solution crystallization and decreasing pollution and airborne dust can not only also greatly reduce production cost without the need to the novel process of machinery and additive shaping, to the production of potassium sulfate, there is realistic meaning.
Summary of the invention
The object of the invention is by pollution-free, the little and reactive crystallization that is low cost of energy consumption prepares the potassium sulfate crystal of Large stone.The present invention the schoenite extracted from salt lake brine and Repone K are reacted directly from solution crystallization produce the potassium sulfate of Large stone, it comprises the process of two aspects: the growth of potassium sulfate crystal in schoenite and Repone K metathesis preparing potassium sulfate and solution.The present invention is with the balance mother liquor bottoming of potassium sulfate, and when adding the mixed slurry of schoenite and Repone K in mother liquor gradually, the two reaction generates potassium sulfate and forms supersaturated solution, produces impellent and makes potassium sulfate crystalline growth.Meanwhile control the degree of super saturation of solution by controlling feed rate, prevent nucleation rate too fast, grain size number is meticulous.And because achieve the recycle of one, two section of mother liquor, decrease the waste of raw material, improve K
+the rate of recovery.
Technical scheme of the present invention is:
Utilize reactive crystallization to produce a method for Large stone potassium sulfate, comprise the following steps:
The first step: one section of crystallization---the reactive crystallization of potassium sulfate
It is schoenite according to mass ratio: the proportioning of Repone K=1:0.6 ~ 0.75, schoenite and Repone K are mixed, then using it directly as material or stand-by as material after adding mother liquor A again, wherein, the quality of the mother liquor A added, is less than or equal to 2 times of schoenite and Repone K quality sum; Take the mother liquor B of 0.1 ~ 5 times of schoenite quality more in addition, without crystal seed or under having crystal seed to add the condition of mother liquor B, material is above being added, material be stir condition under added mother liquor B gradually in 0.5 ~ 2 hour, and make temperature remain on 45 DEG C ~ 60 DEG C constant;
Directly stir 0 ~ 2 hour after reinforced end, or continue stirring after adding water 0 ~ 2 hour, wherein amount of water is less than or equal to 2 times of schoenite quality, when stirring, water was added in above-mentioned slurry in 0.1 ~ 2 hour gradually, finally by obtaining thick potassium and one section of mother liquor after solid-liquid separation, thick potassium is as next step raw material, and one section of mother liquor can as the mother liquor A recycle of the first step in next circulating reaction;
Second step: two sections of crystallizations---the growth of potassium sulfate
Take the water of 0.1 ~ 3 times of schoenite quality in the first step, first the thick potassium that half water and the first step obtain is mixed, and temperature maintains 45 DEG C ~ 60 DEG C, then more remaining water was added gradually in 0.1 ~ 2 hour under the condition constantly stirred, leave standstill 0 ~ 30min, solid-liquid separation again, obtains solid and two sections of mother liquors, and the two sections of mother liquors obtained can as the mother liquor B recycle of the first step in next circulating reaction; Gained solid is through centrifugal, dry, obtains the Large stone potassium sulfate of median size more than 250 μm.
The mass percent of described mother liquor A composition is: K
+=9.03 ~ 10.33%, Mg
2+=2.03 ~ 3.17%, Cl
-=13.48 ~ 15.76%, SO
4 2-=3.01 ~ 6.23% and Na
+=0.10 ~ 1.10%, all the other are water;
The source of described mother liquor A is that one of following three kinds of schemes are any: scheme one: directly formulated for choosing raw material according to the composition of mother liquor A; Or, scheme two: directly can adopt when the composition of mother liquor A above the composition of one section of mother liquor meets, realize recycle; Or scheme three: if the one-tenth that the composition of obtain one section of mother liquor does not meet mother liquor A is grouped into, adds in raw material to one section of mother liquor and makes it form within the compositing range of mother liquor A, realize recycle.
The mass percent of described mother liquor B component is: K
+=6.34 ~ 9.10%, Mg
2+=0 ~ 1.02%, Cl
-=0 ~ 7.83%, SO
4 2-=5.06 ~ 8.49% and Na
+=0 ~ 1.40%, all the other are water;
The source of described mother liquor B is that one of following three kinds of schemes are any: scheme one: directly formulated for choosing raw material according to the composition of mother liquor B; Or, scheme two: directly can adopt when the composition of mother liquor B above described two sections of mother liquor compositions meet, realize recycle; Or scheme three, when the one-tenth that the composition of two sections of mother liquors exceeds mother liquor B be grouped into or mass deficiency time, add raw material and make the composition of two sections of mother liquors within the composition and amount ranges of mother liquor B and meet consumption, realize its recycle.
Described raw material is MgSO
4, MgSO
47H
2o, K
2sO
4, KCl, MgCl
2, MgCl
26H
2o, Na
2sO
4, NaCl and H
2one or more in O, the proportioning between its consumption and material, according to meeting composition and the consumption of mother liquor A or mother liquor B, adopts conventional materials accounting method well known in the art and obtains.
Described crystal seed is potassium sulfate, and median size is 125 ~ 150um, and the add-on of crystal seed is 0.007 ~ 0.07 times of schoenite quality.
Advantage of the present invention is: the schoenite 1. adopted in raw material refines to obtain from the salt lake brine that potassium resource enriches, aboundresources, cheap.2. the recycle of raw material, comprises the recycling of one section of mother liquor and two sections of mother liquors, improves the rate of recovery of potassium ion, decrease the waste of raw material.3. the present invention adopts reactive crystallization to prepare potassium sulfate and the direct crystal obtaining Large stone from solution, and this process cleans is pollution-free, simple to operate, is convenient to suitability for industrialized production.
Compared with prior art, the marked improvement that the present invention utilizes schoenite to prepare the method for Large stone potassium sulfate is, the mean particle size of general powdered potassium sulfate is at below 90um on the market, and the median size of the product potassium sulfate crystal of gained of the present invention can reach more than 250 μm, the K in potassium sulfate
2o can reach more than 51%, meets the standard-required of the top grade product of salt-water system technique potassium sulfate for agricultural use.And abundant raw material of the present invention is easy to get, technique is simple and the recycling of raw material greatly reduces the production cost of potassium sulfate.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is 50 DEG C of K referenced by the present invention
+, Mg
2-//Cl
-, SO
4 2--H
2the metastable phase diagram of O
Fig. 2 is the particle size distribution figure of potassium sulfate in embodiment 1
Fig. 3 is the particle size distribution figure of potassium sulfate in embodiment 2
Fig. 4 is the particle size distribution figure of potassium sulfate in embodiment 3
Fig. 5 is the particle size distribution figure of potassium sulfate in embodiment 4
Fig. 6 is the particle size distribution figure of potassium sulfate in embodiment 5
Embodiment
Fig. 1 is 50 DEG C of K of reference
+, Mg
2-//Cl
-, SO
4 2--H
2the metastable phase diagram of O, wherein:
Total saturation point E
1, balance solid phase is K
2sO
4+ KCl+K
2sO
4mgSO
44H
2o, balance liquid phase composite is: w (K
+) 8.27%, w (Mg
2+) 3.82%, w (Cl
-) 14.94%, w (SO
4 2-) 0.16%;
Total saturation point E
2, balance solid phase is KCl+KClMgSO
46H
2o+K
2sO
4mgSO
44H
2o, balance liquid phase composite is: w (K
+) 4.45%, w (Mg
2+) 6.04%, w (Cl
-) 16.65%, w (SO
4 2-) 0.30%;
Total saturation point E
3, balance solid phase is MgSO
44H
2o+MgSO
46H
2o+K
2sO
4mgSO
44H
2o, balance liquid phase composite is: w (K
+) 1.99%, w (Mg
2+) 6.82%, w (Cl
-) 11.38%, w (SO
4 2-) 0.45%;
Total saturation point E
4, balance solid phase is MgSO
44H
2o+KClMgSO
46H
2o+K
2sO
4mgSO
44H
2o, balance liquid phase composite is: w (K
+) 1.85%, w (Mg
2+) 7.49%, w (Cl
-) 16.95%, w (SO
4 2-) 0.40%;
Total saturation point E
5, balance solid phase is KCl+KClMgSO
46H
2o+KClMgCl
26H
2o, balance liquid phase composite is: w (K
+) 2.24%, w (Mg
2+) 7.65%, w (Cl
-) 21.73%, w (SO
4 2-) 0.15%;
Total saturation point E
6, balance solid phase is KCl+MgSO
44H
2o+KClMgCl
26H
2o, balance liquid phase composite is: w (K
+) 0.10%, w (Mg
2+) 9.56%, w (Cl
-) 26.56%, w (SO
4 2-) 0.05%;
Ar，K
2SO
4；Syl，KCl；Hex，MgSO
4·6H
2O；Tet，MgSO
4·4H
2O；Bis，MgCl
2·6H
2O；
Leo，K
2SO
4·MgSO
4·4H
2O；Kai，KCl·MgSO
4·6H
2O；Car，KCl·MgCl
2·6H
2O
The conversion essence of schoenite and Repone K is water salt dissolution equilibrium process, and its theoretical foundation is K
+, Mg
2-//Cl
-, SO
4 2--H
2the Phase Diagram for Aqueous Salt Solutions of O, as shown in Figure 1, analyzes known from figure, 50 DEG C time, schoenite M point and Repone K A react, according to lever principle, when material point is P point, the rate of recovery of potassium sulfate is the highest, applies material balance principle, can be obtained the material relationships of conversion by simultaneous equations.As table 1 institute
Under table 150 DEG C condition, schoenite and Repone K transform the material relationships (g) of preparing potassium sulfate
Mother liquor A composition described below will reach following compositing range: mass percent is: K
+=9.03 ~ 10.33%, Mg
2+=2.03 ~ 3.17%, Cl
-=13.48 ~ 15.76%, SO
4 2-=3.01 ~ 6.23% and Na
+=0.10 ~ 1.10%, all the other are water;
Described mother liquor B component will reach following compositing range: mass percent is: K
+=6.34 ~ 9.10%, Mg
2+=0 ~ 1.02%, Cl
-=0 ~ 7.83%, SO
4 2-=5.06 ~ 8.49% and Na
+=0 ~ 1.40%, all the other are water.
Embodiment 1
The first step: one section of crystallization---the reactive crystallization of potassium sulfate
First schoenite 150g and Repone K 100.5g is mixed, stand-by as material.Preparation 220g mother liquor B also remains on 50 DEG C, wherein mother liquor B consist of mass percent: K
+=6.34%, SO
4 2-=7.81%, all the other are that water is (by 31.16gK
2sO
4and 188.84gH
2o preparation.Then under the condition constantly stirred, the material mixed was added in mother liquor B gradually in 0.5 hour, and temperature of reaction keep 50 DEG C constant.Added in above-mentioned slurry by the water of 52.6g gradually in 0.5 hour again after reinforced end, after adding water and terminating, continue stirring 1 hour, last solid-liquid separation obtains thick potassium 141.2g and section mother liquor 367.1g, and thick potassium is as the raw material of second step.Wherein, the ion component contained by one section of mother liquor: K
+=9.95%, Mg
2+=2.51, Cl
-=14.60%, SO
4 2-=4.02% and Na
+=0.75%, all the other are water.
Second step: two sections of crystallizations---the growth of potassium sulfate
Take the water of 112.8g, first mixed by the thick potassium that half water and upper step are obtained by reacting, and temperature of reaction maintains 50 DEG C, then when constantly stirring, then added gradually by second half water, the time of adding water is 0.5 hour.After two sections of end that add water, leave standstill 1min, again solid-liquid separation, obtain product and two sections of mother liquors, product carries out centrifugal, dries, and the quality product after drying is 111.2g, and two sections of mother liquor quality are 137.4g, and the mother liquor B as next cycle recycles.Wherein, the composition of two sections of mother liquors: K
+=8.14%, Mg
2+=0.90%, Cl
-=6.11%, SO
4 2-=6.17% and Na
+=0.38%, all the other are water.
Two sections of mother liquors of gained can be used as new mother liquor B, and two sections of mother liquors and mother liquor B meet following compositing range: K
+=6.34 ~ 9.10%, Mg
2+=0 ~ 1.02%, Cl
-=0 ~ 7.83%, SO
4 2-=5.06 ~ 8.49% and Na
+=0 ~ 1.40%, all the other are water.When recycling, if the composition of obtain two sections of mother liquors exceed above-mentioned one-tenth be grouped into or quality can not meet the first step reaction consumption, need add suitable raw material make the composition of two sections of mother liquors above-mentioned one-tenth be grouped into the first step reaction amount ranges within and meet consumption, realize recycle.
In the present embodiment, the median size of product potassium sulfate crystal is 277.629 μm, and in product, potassium sulfate content reaches 94.5%, and purity meets the standard-required of the top grade product of the potassium sulfate for agricultural use of national regulation.Fig. 2 is the particle size distribution figure of potassium sulfate under this example laboratory condition, and in figure, the size of potassium sulfate crystal is mainly distributed in about 277.629 μm, and size-grade distribution is concentrated.
Embodiment 2
The first step: one section of crystallization---the reactive crystallization of potassium sulfate
Mother liquor A50g, schoenite 150g and Repone K 100.5g are mixed and is made into slurry stand-by (aftermentioned abbreviation wet feed slurry).The composition mass percent of the mother liquor A wherein prepared: K
+=9.95%, Mg
2+=2.51, Cl
-=14.65%, SO
4 2-=4.05% and Na
+=0.75%, all the other are that water is (by 2.53gMgSO
4, 9.50gKCl, 6.33gMgCl
26H
2o, 0.96gNaCl and 30.68gH
2o preparation).The potassium sulfate crystal seed (crystal seed mean particle size is 125-150 μm) taking 10g joins in the mother liquor B of 220g preparation, the composition mass percent of the mother liquor B wherein prepared: K
+=8.14%, Mg
2+=0.90%, Cl
-=6.11%, SO
4 2-=6.17% and Na
+=0.39%, all the other are that water is (by 9.90gMgSO
4, 10.25gK
2sO
4, 25.41gKCl, 2.20gNaCl and 172.24gH
2o preparation).Then under the condition constantly stirred, wet feed is starched and added gradually in mother liquor B in 1.5 hours, and temperature maintains 50 DEG C.Again the water of 52.6g was added in above-mentioned slurry in 0.5 hour gradually after reinforced end, stirring is continued 1 hour after adding water and terminating, finally by obtaining thick potassium 160.2g and section mother liquor 410.1g after solid-liquid separation, thick potassium is as the raw material of second step, and one section of mother liquor is as next cycle mother liquor A recycle.Ion component contained by one section of mother liquor: K
+=9.97%, Mg
2+=2.54, Cl
-=14.60%, SO
4 2-=4.02% and Na
+=0.36%, all the other are water, meet the composition compositing range of mother liquor A: K
+=9.03 ~ 10.33%, Mg
2+=2.03 ~ 3.17%, Cl
-=13.48 ~ 15.76%, SO
4 2-=3.01 ~ 6.23% and Na
+=0.10 ~ 1.10%, all the other are water.
Second step: two sections of crystallizations---the growth of potassium sulfate
Take the water of 112.8g, first mixed with one section of thick potassium be obtained by reacting by half water, and temperature maintains 50 DEG C, then when constantly stirring, then added gradually by second half water, the time of adding water is 0.5 hour.After two sections of end that add water, leave standstill 5min, again solid-liquid separation, obtain product and two sections of mother liquors, product carries out centrifugal, dries.Quality product after drying is 119.2g, and to be 143.8g recycle as the mother liquor B of next cycle for two sections of mother liquors, the ion component wherein contained by two sections of mother liquors: K
+=8.14%, Mg
2+=0.90%, Cl
-=6.11%, SO
4 2-=6.17% and Na
+=0.38%, all the other are water, meet the composition compositing range of mother liquor B: K
+=6.34 ~ 9.10%, Mg
2+=0 ~ 1.02%, Cl
-=0 ~ 7.83%, SO
4 2-=5.06 ~ 8.49% and Na
+=0 ~ 1.40%, all the other are water.
In the present embodiment, the median size of product potassium sulfate crystal is 336.443 μm, even particle size distribution, and in product, potassium sulfate content reaches 94.9%, and purity meets the standard-required of the top grade product of the potassium sulfate for agricultural use of national regulation.Fig. 3 is the particle size distribution figure of potassium sulfate under this example laboratory condition, and in figure, the size of potassium sulfate crystal is mainly distributed in about 336.443 μm, and size-grade distribution is concentrated.
Embodiment 3
The first step: one section of crystallization---the reactive crystallization of potassium sulfate
One section of mother liquor 50g, schoenite 150g that meeting of taking that the first step in embodiment 2 obtains, mother liquor A formed and Repone K 100.5g mix stand-by, what take that 10g potassium sulfate crystal seed (crystal seed mean particle size is 125-150 μm) joins that second step in 220g embodiment 2 obtains meets in two sections of mother liquors that mother liquor B forms, because the two sections of mother liquors obtained in embodiment 2 can not meet this consumption, on the basis that the two sections of mother liquor 143.8g obtained in whole embodiment 2 are all used, then need to add 3.42gMgSO
4, 3.57gK
2sO
4, 8.79gKCl, 0.77gNaCl and 59.65gH
2o is made into the mother liquor B of 220g, then starched by wet feed under the condition constantly stirred and added gradually in two sections of mother liquors in 1.5 hours, and temperature maintains 50 DEG C.Again the water of 52.6g was added in above-mentioned slurry in 0.5 hour gradually after reinforced end, after adding water and terminating, continue stirring 1 hour, finally by obtaining thick potassium 157.0g and section mother liquor 411.8g after solid-liquid separation.Thick potassium is as the raw material of second step, and one section of mother liquor recycles as next cycle mother liquor A.Ion component contained by one section of mother liquor: K
+=9.96%, Mg
2+=2.53, Cl
-=14.60%, SO
4 2-=4.02% and Na
+=0.036%, all the other are water, meet the composition compositing range of mother liquor A: K
+=9.03 ~ 10.33%, Mg
2+=2.03 ~ 3.17%, Cl
-=13.48 ~ 15.76%, SO
4 2-=3.01 ~ 6.23% and Na
+=0.10 ~ 1.10%, all the other are water.
Second step: two sections of crystallizations---the growth of potassium sulfate
Take the water of 112.8g, first mixed with one section of thick potassium be obtained by reacting by half water, and temperature maintains 50 DEG C, then when constantly stirring, then added gradually by second half water, the time of adding water is 0.5 hour.After two sections of end that add water, leave standstill 5min, again solid-liquid separation, obtain product and two sections of mother liquors, product carries out centrifugal, dries.Quality product after drying is 110.7g, and to be 140.8g recycle as the mother liquor B of next cycle for two sections of mother liquors, the ion component wherein contained by two sections of mother liquors: K
+=8.15%, Mg
2+=0.90%, Cl
-=6.11%, SO
4 2-=6.16% and Na
+=0.38%, all the other are water.Meet the composition compositing range of mother liquor B: K
+=6.34 ~ 9.10%, Mg
2+=0 ~ 1.02%, Cl
-=0 ~ 7.83%, SO
4 2-=5.06 ~ 8.49% and Na
+=0 ~ 1.40%, all the other are water.
In the present embodiment, the median size of product potassium sulfate crystal is 371.886 μm, even particle size distribution, and in product, potassium sulfate content reaches 95.0%, and purity meets the standard-required of the top grade product of the potassium sulfate for agricultural use of national regulation.Fig. 4 is the particle size distribution figure of potassium sulfate under this example laboratory condition, and in figure, the size of potassium sulfate crystal is mainly distributed in about 371.886 μm, and size-grade distribution is more concentrated.
Embodiment 4
The first step: one section of crystallization---the reactive crystallization of potassium sulfate
Mother liquor A50g, schoenite 150g and Repone K 100.5g are mixed and is made into slurry stand-by (aftermentioned abbreviation wet feed slurry).The composition mass percent of the mother liquor A wherein prepared: K
+=9.95%, Mg
2+=2.51, Cl
-=14.65%, SO
4 2-=4.05% and Na
+=0.75%, all the other are that water is (by 2.53gMgSO
4, 9.50gKCl, 6.33gMgCl
26H
2o, 0.96gNaCl and 30.68gH
2o preparation).The crystal seed (median size of crystal seed is 125 μm-150 μm) taking 5g adds in the mother liquor B of 250g preparation, the composition mass percent of the mother liquor B wherein prepared: K
+=6.90%, SO
4 2-=8.49%, all the other are that water is (by 33.87gK
2sO
4and 186.13gH
2o preparation).Then under the condition constantly stirred, wet feed is starched and added gradually in two sections of mother liquors in 2 hours, and temperature keep 60 DEG C constant.Continue stirring 2 hours after reinforced end, obtain thick potassium 158.9g and section mother liquor 380.0g finally by solid-liquid separation, thick potassium is as the raw material of second step, and one section of mother liquor recycles as next cycle mother liquor A.Ion component contained by one section of mother liquor: K
+=9.98%, Mg
2+=2.54%, Cl
-=14.56%, SO
4 2-=4.02% and Na
+=0.37%, all the other are water, meet the composition compositing range of mother liquor A: K
+=9.03 ~ 10.33%, Mg
2+=2.03 ~ 3.17%, Cl
-=13.48 ~ 15.76%, SO
4 2-=3.01 ~ 6.23% and Na
+=0.10 ~ 1.10%, all the other are water.
Second step: two sections of crystallizations---the growth of potassium sulfate
Take the water of 176.3, first mixed with one section of thick potassium be obtained by reacting by half water, and temperature maintains 60 DEG C, then under the condition constantly stirred, then added gradually by second half water, the time of adding water is 1 hour.After two sections of end that add water, leave standstill 5min, again solid-liquid separation, obtain product and two sections of mother liquors, product carries out centrifugal, dries.Quality product after drying is 116.1g, and to be 210.2g recycle as the mother liquor B of next cycle for two sections of mother liquors, the ion component wherein contained by two sections of mother liquors: K
+=8.15%, Mg
2+=0.91%, Cl
-=6.11%, SO
4 2-=6.17% and Na
+=0.37%, all the other are water, meet the composition compositing range of mother liquor B: K
+=6.34 ~ 9.10%, Mg
2+=0 ~ 1.02%, Cl
-=0 ~ 7.83%, SO
4 2-=5.06 ~ 8.49% and Na
+=0 ~ 1.40%, all the other are water.
In the present embodiment, the median size of product potassium sulfate crystal is 396.237 μm, and product granularity is even, and in product, potassium sulfate content reaches 94.5%, and purity meets the standard-required of the top grade product of the potassium sulfate for agricultural use of national regulation.Fig. 5 is the particle size distribution figure of potassium sulfate under this example laboratory condition, and in figure, the size of potassium sulfate crystal is mainly distributed in about 396.237 μm, and size-grade distribution is concentrated.
Embodiment 5
The first step: one section of crystallization---the reactive crystallization of potassium sulfate
The one section of mother liquor 50g, the schoenite 150g that meet solution A that the first step in embodiment 4 are obtained and Repone K 100.5g mix and are made into slurry stand-by (aftermentioned abbreviation wet feed slurry).The crystal seed (median size of crystal seed is 125 μm-150 μm) taking 5g adds in 250g to mother liquor B, because the two sections of mother liquors obtained in embodiment 4 can not meet this consumption, on the basis that the two sections of mother liquor 210.2g obtained in whole embodiment 4 are all used, then need to add 1.79gMgSO
4, 1.86gK
2sO
4, 4.59gKCl, 0.40gNaCl and 31.16gH
2o is made into the mother liquor B of 250g, is then starched by wet feed under the condition constantly stirred and adds gradually in two sections of mother liquors in 2 hours, and temperature keep 60 DEG C constant.Continue stirring 2 hours after reinforced end, obtain thick potassium 158.9g and section mother liquor 380.0g finally by solid-liquid separation, thick potassium is as the raw material of second step, and one section of mother liquor recycles as next cycle mother liquor A.Ion component contained by one section of mother liquor: K
+=9.96%, Mg
2+=2.54%, Cl
-=14.60%, SO
4 2-=4.02% and Na
+=0.037%, all the other are water, meet the composition compositing range of mother liquor A: K
+=9.03 ~ 10.33%, Mg
2+=2.03 ~ 3.17%, Cl
-=13.48 ~ 15.76%, SO
4 2-=3.01 ~ 6.23% and Na
+=0.10 ~ 1.10%, all the other are water.
Second step: two sections of crystallizations---the growth of potassium sulfate
Take the water of 176.3, first mixed with one section of thick potassium be obtained by reacting by half water, and temperature maintains 60 DEG C, then under the condition constantly stirred, then added gradually by second half water, the time of adding water is 1 hour.After two sections of end that add water, leave standstill 5min, again solid-liquid separation, obtain product and two sections of mother liquors, product carries out centrifugal, dries.Quality product after drying is 120.1g, and to be 215.2g recycle as the mother liquor B of next cycle for two sections of mother liquors, the ion component wherein contained by two sections of mother liquors: K
+=8.15%, Mg
2+=0.91%, Cl
-=6.12%, SO
4 2-=6.17% and Na
+=0.37%, all the other are water, meet the composition compositing range of mother liquor B: K
+=6.34 ~ 9.10%, Mg
2+=0 ~ 1.02%, Cl
-=0 ~ 7.83%, SO
4 2-=5.06 ~ 8.49% and Na
+=0 ~ 1.40%, all the other are water.
In the present embodiment, the median size of product potassium sulfate crystal is 400.259 μm, and product granularity is even, and in product, potassium sulfate content reaches 95.1%, and purity meets the standard-required of the top grade product of the potassium sulfate for agricultural use of national regulation.Fig. 6 is the particle size distribution figure of potassium sulfate under this example laboratory condition, and in figure, the size of potassium sulfate crystal is mainly distributed in about 400.259 μm, and size-grade distribution is concentrated.
Unaccomplished matter of the present invention is known technology.
Claims (5)
1. utilize reactive crystallization to produce a method for Large stone potassium sulfate, it is characterized by and comprise the following steps:
The first step: one section of crystallization---the reactive crystallization of potassium sulfate
It is schoenite according to mass ratio: the proportioning of Repone K=1:0.6 ~ 0.75, schoenite and Repone K are mixed, then using it directly as material or stand-by as material after adding mother liquor A again, wherein, the quality of the mother liquor A added, is less than or equal to 2 times of schoenite and Repone K quality sum; Take the mother liquor B of 0.1 ~ 5 times of schoenite quality more in addition, without crystal seed or under having crystal seed to add the condition of mother liquor B, material is above being added, material be stir condition under added mother liquor B gradually in 0.5 ~ 2 hour, and make temperature remain on 45 DEG C ~ 60 DEG C constant;
Directly stir 0 ~ 2 hour after reinforced end, or continue stirring after adding water 0 ~ 2 hour, wherein amount of water is less than or equal to 2 times of schoenite quality, in situation about stirring, water was added gradually in above-mentioned slurry in 0.1 ~ 2 hour, finally by obtaining thick potassium and one section of mother liquor after solid-liquid separation, thick potassium is as next step raw material, and one section of mother liquor can as the mother liquor A recycle of the first step in next circulating reaction;
Second step: two sections of crystallizations---the growth of potassium sulfate
Take the water of 0.1 ~ 3 times of schoenite quality in the first step, first the thick potassium that half water and the first step obtain is mixed, and temperature maintains 45 DEG C ~ 60 DEG C, then more remaining water was added gradually in 0.1 ~ 2 hour under the condition constantly stirred, leave standstill 0 ~ 30min, carry out two sections of crystallizations, again solid-liquid separation, obtain solid and two sections of mother liquors, the two sections of mother liquors obtained can as the mother liquor B recycle of the first step in next circulating reaction; Gained solid is through centrifugal, dry, obtains the Large stone potassium sulfate of median size more than 250 μm;
The mass percent of described mother liquor A composition is: K
+=9.03 ~ 10.33%, Mg
2+=2.03 ~ 3.17%, Cl
-=13.48 ~ 15.76%, SO
4 2-=3.01 ~ 6.23% and Na
+=0.10 ~ 1.10%, all the other are water;
The mass percent of described mother liquor B component is: K
+=6.34 ~ 9.10%, Mg
2+=0 ~ 1.02%, Cl
-=0 ~ 7.83%, SO
4 2-=5.06 ~ 8.49% and Na
+=0 ~ 1.40%, all the other are water.
2. utilize reactive crystallization to produce the method for Large stone potassium sulfate as claimed in claim 1, the source that it is characterized by described mother liquor A is that one of following three kinds of schemes are any: scheme one: directly formulated for choosing raw material according to the composition of mother liquor A; Or, scheme two: directly can adopt when the composition of mother liquor A above the composition of one section of mother liquor meets, realize recycle; Or scheme three: if the one-tenth that the composition of obtain one section of mother liquor does not meet mother liquor A is grouped into, adds in raw material to one section of mother liquor and makes it form within the compositing range of mother liquor A, realize recycle.
3. utilize reactive crystallization to produce the method for Large stone potassium sulfate as claimed in claim 1, the source that it is characterized by described mother liquor B is that one of following three kinds of schemes are any: scheme one: directly formulated for choosing raw material according to the composition of mother liquor B; Or, scheme two: directly can adopt when the composition of mother liquor B above described two sections of mother liquor compositions meet, realize recycle; Or, scheme three, when the one-tenth that the composition of two sections of mother liquors exceeds mother liquor B be grouped into or mass deficiency time, add raw material and make the composition of two sections of mother liquors within the composition and amount ranges of mother liquor B and meet consumption, realize its recycle.
4. the reactive crystallization that utilizes as described in Claims 2 or 3 produces the method for Large stone potassium sulfate, and it is characterized by described raw material is MgSO
4, MgSO
47H
2o, K
2sO
4, KCl, MgCl
2, MgCl
26H
2o, Na
2sO
4, NaCl and H
2one or more in O, the proportioning between its consumption and material, according to meeting composition and the consumption of mother liquor A or mother liquor B, adopting conventional materials accounting method and obtaining.
5. utilize reactive crystallization to produce the method for Large stone potassium sulfate as claimed in claim 1, it is characterized by described crystal seed is potassium sulfate, and median size is 125 ~ 150 μm, and the add-on of crystal seed is 0.007 ~ 0.07 times of schoenite quality.
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| CN104743583B (en) * | 2015-04-24 | 2017-03-08 | 傅培鑫 | A kind of method that utilization potassium alum produces potassium sulfate and aluminum chloride |
| CN105217657A (en) * | 2015-08-27 | 2016-01-06 | 莫红兵 | A kind of potassium sulfate crystal growth stimulant and application |
| CN105948080A (en) * | 2015-11-23 | 2016-09-21 | 湖南衡阳新澧化工有限公司 | Preparation method of large grained anhydrous sodium sulfate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089576A (en) * | 1993-01-08 | 1994-07-20 | 中国科学院青海盐湖研究所 | A kind of preparation method of vitriolate of tartar |
| CN1132180A (en) * | 1995-03-30 | 1996-10-02 | 杨大敏 | Method for prodn. of potassium sulfate by NaSO4 and KCl through metathesis |
| CN1281822A (en) * | 2000-08-29 | 2001-01-31 | 化学工业部连云港设计研究院 | Method for preparing potassium sulfate by using sulfate type potassium-containing bittern |
| CN1785810A (en) * | 2004-12-06 | 2006-06-14 | 沙启志 | One step method for production of potassium sulphate using extraction crystallization reaction |
| CN102674405A (en) * | 2012-05-30 | 2012-09-19 | 河北工业大学 | Method for preparing potassium sulfate by using picromerite |
-
2013
- 2013-09-23 CN CN201310436468.0A patent/CN103466662B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089576A (en) * | 1993-01-08 | 1994-07-20 | 中国科学院青海盐湖研究所 | A kind of preparation method of vitriolate of tartar |
| CN1132180A (en) * | 1995-03-30 | 1996-10-02 | 杨大敏 | Method for prodn. of potassium sulfate by NaSO4 and KCl through metathesis |
| CN1281822A (en) * | 2000-08-29 | 2001-01-31 | 化学工业部连云港设计研究院 | Method for preparing potassium sulfate by using sulfate type potassium-containing bittern |
| CN1785810A (en) * | 2004-12-06 | 2006-06-14 | 沙启志 | One step method for production of potassium sulphate using extraction crystallization reaction |
| CN102674405A (en) * | 2012-05-30 | 2012-09-19 | 河北工业大学 | Method for preparing potassium sulfate by using picromerite |
Non-Patent Citations (1)
| Title |
|---|
| "反应结晶法制取颗粒硫酸钾的研究进展";张宁等;《无机盐工业》;20080531;第40卷(第5期);第5-8页 * |
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