CN105060329B - Method for producing picromerite by taking potassium chloride and mirabilite as raw materials - Google Patents
Method for producing picromerite by taking potassium chloride and mirabilite as raw materials Download PDFInfo
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- CN105060329B CN105060329B CN201510483797.XA CN201510483797A CN105060329B CN 105060329 B CN105060329 B CN 105060329B CN 201510483797 A CN201510483797 A CN 201510483797A CN 105060329 B CN105060329 B CN 105060329B
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- picromerite
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- mirabilite
- potassium chloride
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Abstract
The present invention relates to a method for producing picromerite by taking potassium chloride and mirabilite as raw materials. The method comprises the following steps of: firstly, dissolving mirabilite; eliminating insoluble substances; cooling and performing crystallization to obtain mirabilite decahydrate; then, converting the mirabilite decahydrate and the potassium chloride at the room temperature to obtain mirabilite potassium slurry; performing solid-liquid separation on the mirabilite potassium slurry to obtain mirabilite potassium and mirabilite potassium mother liquor; converting the mirabilite potassium with carnallite and magnesium sulfate in a picromerite saturation solution at the room temperature so as to obtain picromerite slurry, and obtaining a picromerite product through solid-liquid separation; and recovering potassium mixed salt from the mirabilite potassium mother liquor and excessive picromerite mother liquor through a salt pan. The process provided by the present invention is simple, and the whole processing process has no three-waste problem, thereby providing another way for processing and preparing picromerite by use of salt lake resources.
Description
Technical field
The invention belongs to inorganic chemicals industry field, more particularly to a kind of with potassium chloride, saltcake conversion production glaserite, potassium
Saltcake and carnallite, the production technology of epsom salt production picromerite (potash magnesium sulphate fertilizer).
Background technology
Picromerite (potash magnesium sulphate fertilizer) can as a kind of multi-element K fertilizer, in addition to containing potassium, sulphur, magnesium, also containing calcium,
The elements such as silicon, boron, iron, zinc, in alkalescent, are particularly suitable for acid ground administration, typically make base manure, also can topdress.It is applied to
The crops such as paddy rice, corn, sugarcane, peanut, tobacco, potato, beet, water fruits and vegetables, clover.With the list for waiting potassium amount (K2O)
Matter potash fertilizer potassium chloride, potassium sulfate are compared, and the application effect of agricultural potassium sulfate magnesium is better than potassium chloride, slightly better than potassium sulfate.
At present, the preparation method of picromerite mainly produces soft potassium magnesium by raw material conversion floatation of salt pan potassium mixed salt
Alum.Picromerite is not only in itself a kind of chlorideless potassic fertilizer, still prepares the intermediate products of potassium sulfate.
Producing in the method for picromerite by raw material conversion method of potassium mixed salt, first potassium mixed salt must grind, and make thing
Material particle diameter 100% crosses 60 mesh, and in order to be converted into picromerite, then again flotation obtains picromerite, although the method stream
Journey is simple, but the rate of recovery of potassium is low, and the yield of potassium only has 55-60%.
With in potassium chloride, the method for saltcake production potassium sulfate, generally potassium sulfate, the first step are produced using two-step method
Conversion：By potassium chloride and saltcake with certain proportion mixing, the reaction under the conditions of 25-30 DEG C generates glaserite, second step conversion：
Glaserite is mixed by a certain percentage again with potassium chloride, the reaction under the conditions of 25-30 DEG C generates potassium sulfate.With pure potassium chloride and
Saltcake meter, the yield of whole process potassium, only 57.7%.
Potassium sulfate is produced with potassium chloride, saltcake, finding report is fewer, and whole production process potassium recovery rate is low, in Qinghai
The built ten Duo Jia factories since 80 years last century, close because not producing qualified potassium product.
The content of the invention
The purpose of the present invention is that the agricultural potassium chloride produced at present for China causes the hardening soil, and sulfate potash fertilizer is short
Scarce present situation, there is provided a kind of potassium acquirement rate is high, production capacity is big, and technical process is simple, meets the new of energy-conserving and environment-protective
Picromerite manufacturing technique method.Picromerite is in itself not only a kind of fine chlorideless potassic fertilizer, or the centre of production potassium sulfate
Product, and also solve, product cost low using potassium acquirement rate in saltcake, potassium chloride two-step method production Process of Potassium Sulfate
High problem.The method contributes to the comprehensive utilization of China's salt lake resources and sulfate resource.
The purpose of the present invention can be reached by following measures：
A kind of method for producing picromerite as raw material with potassium chloride and saltcake, it comprises the steps：
A. potassium chloride and sal glauberi and water are pressed into 1：2.3～2.7：0.5～0.8 mass ratio mixing, at 15 DEG C
Reaction is stirred under～50 DEG C of temperature conditionss, separation of solid and liquid respectively obtains glaserite after reaction；
B. the glaserite for obtaining carnallite, epsom salt and step A is by 1：3.0～3.9：3.8～5.0 mass ratio
Example is added in picromerite circulating mother liquor, the stirring reaction at 5 DEG C～35 DEG C, and separation of solid and liquid obtains picromerite product after reaction
Product.
Picromerite mother liquor in the present invention is to have obtained mother after separation of solid and liquid in picromerite saturated aqueous solution or step B
Liquid.When reaction is just started, added as medium in carnallite, epsom salt and the glaserite mixture of step B with fresh water,
To prepare picromerite mother liquor, this mother liquor is used as circulating mother liquor.The mother liquor is the solution to picromerite saturation.
In step, potassium chloride is preferably 1 with the mass ratio of sal glauberi and water：2.45～2.59：0.59～
0.68.Reaction temperature is preferably 15 DEG C～30 DEG C, further preferred 25 DEG C～30 DEG C.Reaction time is 0.5～5 hour, preferably
For 1～3 hour.
In stepb, the potassium content in glaserite affects larger to carnallite and epsom salt proportioning, therefore one
In planting preferred version, the mass ratio of the glaserite that carnallite, epsom salt and step A are obtained is 1：3.19～3.58：3.93
～4.50.Reaction temperature is preferably 15 DEG C～25 DEG C, further preferred 20 DEG C～25 DEG C.Reaction time is 0.5～5 hour, excellent
Elect 1～3 hour as.
The principle of this method is broadly divided into the following aspects：
With saltcake, potassium chloride and water as the composition point of waste glaserite, in K+、Na+//SO4 2-、Cl-- H2O 25℃
It is B points, A points in salt-water system equilbrium phase diagram (see accompanying drawing 1).Saltcake and potassium chloride conversion production glaserite：Batching system point is
AB lines and GC line intersection point F, are to obtain glaserite maximum yield, and liquidus point should be controlled in C points, water distribution (amount of water is calculated with water figure)
Liquidus point is set to be exactly C points, solidus is G points, i.e., pure Na2SO4·3K2SO4Solidus.Raw material reality is pressed in process of the test
Composition calculates saltcake with potassium chloride and the proportion scale of water.
With carnallite, glaserite and magnesium sulfate as waste picromerite, each raw material composition point is in K+、Na+、Mg2+//
SO4 2-、Cl-- H2In 25 DEG C of Quinary system metastable phase diagrams of O：M：Epsom salt solidus；G points：Glaserite solidus；K points：
Carnallite solidus；P points：Picromerite composition point (being specifically shown in accompanying drawing 2).
In P points, i.e., calculate carnallite, epsom salt, the mixed material composition point of glaserite by actual composition is
Picromerite constitutes point, and during with picromerite mother liquor as medium, mixed material is converted into as soft potassium magnesium under normal temperature condition
Alum slip, Jing after separation of solid and liquid solid picromerite and picromerite mother liquor, picromerite both can be used as product, again can be with
Used as the raw material of production potassium sulfate, mother liquor will be recycled, and the evaporation of excess portion lease making adds reclaims potassium mixed salt.
Raw material potassium chloride in the present invention can adopt the agricultural certified products potassium chloride of normal Salt Lake Potash factory production,
Can be using the certified products potassium chloride prepared by additive method or technique.
Raw material saltcake in the present invention includes thenardite and mirabilite hydrate (sal glauberi).In Chaidamu Basin, Qinghai Province
The mirabilite ore of many places is dispersed with, to examine sweat Si Latu, earth's surface mirabilite ore geology proved reserves are more than 7,200,000,000 tons to maximum mirabilite ore,
Mirabilite resource enriches very much, in recovery process, is selectively excavated using simple, so that it may obtain sulfur acid sodium 95% with
On thenardite, but due to the silt impurity containing a few percent, it is non-serviceable to be entrained in the product of production.We
Sal glauberi in method can be by the thenardite of sulfur acid sodium more than 70% (can be with more than 95% sodium sulphate during experiment)
With water in mass ratio 1：After 1.5～2.5 Hybrid Heatings, separate out Jing after sedimentation filtration, natural cooling crystallization and be obtained.Preferably, contain
The thenardite of sodium sulphate more than 95% is 1 with the mass ratio of water：2, heating-up temperature be 33 DEG C～50 DEG C, preferably 33 DEG C～35
DEG C, because maximum during 32.38 DEG C of the solubility of sodium sulphate, separate out Jing after sedimentation filtration, natural cooling crystallization and contain pure more than 99%
Sal glauberi.Certainly this method may also be employed additive method or the sal glauberi prepared by technique.
Raw material carnallite in the present invention is the carnallite of Solar pond production, and it is the raw material for producing potassium chloride.
Raw material epsom salt in the present invention is sulfate type bittern production potassium mixed salt, before carnallite, magnesium sulfate and chlorine
Change the salt-mixture separated out when sodium is satisfied altogether, this material is, as waste, magnesium sulfate twice laid to be made in this technology in salt lake,
Jing bittern in proportion 1：50 DEG C are heated to after 0.6～1.6 mixing, epsom salt is just changed into six water magnesium sulfates, using screening,
Bulky grain sodium chloride is weeded out, screenings cools to less than 48 DEG C, and scrubbed, separation of solid and liquid must epsom salt.
In terms of market, the potassium chloride containing potassium oxide 57% only has 1200 yuan/ton within domestic 2014, and contains potassium oxide and only have
Just up to 1960 yuan/ton, by this technology, (1) can make chlorine potassium fertilizer be converted into chlorideless potassic fertilizer to 24% picromerite, and (2) solve
China's agricultural causes soil compaction problem because a large amount of for many years using containing chlorine potassium fertilizer, and country proposes that agricultural chemicals and potash fertilizer are placed restrictions in this year
Usage amount, (3) part solves the problems, such as that a large amount of magnesium sulfate go out of use in potassium fertilizer production process, reaches the purpose of environmental protection, therefore
This technology tool has been widely used and high promotional value.
This method flow process is simple, does not use floating agent, also non-sodium chloride separation circuit, Jing after two step conversion reactions, directly
Connect and obtain the wet product of picromerite.
Description of the drawings
Fig. 1 is Na+、K+//SO4 2-、Cl-- H2Equilbrium phase diagram during 25 DEG C of O systems；
G points are Na in figure2SO4·3K2SO4The solidus of glaserite.
Fig. 2 is K+、Na+、Mg2+//SO4 2-、Cl-- H225 DEG C of Quinary system metastable phase diagrams of O；
In figure, M is epsom salt solidus, and K is carnallite solidus, and G is glaserite solidus, and P is picromerite
Solidus.
Fig. 3 is a kind of process chart of the present invention.
Specific embodiment
Embodiment 1：
Potassium chloride 1000g, mirabilite hydrate：2590g, water：600ml, stirs and is heated to 30 DEG C after mixing, then natural
Cooling, stirs 2 hours, and material reaction temperature is down to 25 DEG C, and Jing separation of solid and liquid obtains 1505.6 grams of solid glaserite, and glaserite is female
1640 milliliters of liquid.The conversion acquirement rate of potassium is：83.68%.Material composition is shown in Table 1：
With 400 grams of above-mentioned glaserite, then add 100 grams of carnallite, 313.8 grams of epsom salt is added after mixing
In 1500ml20-25 DEG C of circulating mother liquor, slip separation of solid and liquid is obtained 603 grams of picromerite and soft potassium magnesium by stirring reaction 2 hours
1600 milliliters of alum saturated solution, the acquirement rate of potassium is 93.50%.Material composition is shown in Table 2.
Total acquirement rate of whole process potassium is：79.76%.
Table 1
Table 2
Embodiment 2：
Potassium chloride 1000g, mirabilite hydrate：2470g, water：660ml, stirring at normal temperature is reacted 2 hours after mixing, Jing solid-liquids point
From obtaining 1294 grams of solid glaserite, 1900 milliliters of glaserite mother liquor.Material composition is shown in Table 3.
With 387.7 grams of above-mentioned glaserite, then add 100 grams of carnallite, 317.2 grams of epsom salt is added after mixing
In 1500ml 20-25 DEG C circulating mother liquors, slip separation of solid and liquid is obtained 602 grams of picromerite and soft potassium magnesium by stirring reaction 2 hours
1590 milliliters of alum saturated solution, the acquirement rate of potassium is 91.68%.Material composition is shown in Table 4.
Total acquirement rate of whole process potassium is：75.75%.
Table 3
Table 4
Claims (6)
1. it is a kind of with potassium chloride and saltcake as the method for raw material production picromerite, it is characterised in that to comprise the steps：
A. potassium chloride and sal glauberi and water are pressed into 1：2.3～2.7：0.5～0.8 mass ratio mixing, 25 DEG C～30
Reaction is stirred under DEG C temperature conditionss, separation of solid and liquid obtains glaserite after reaction；
B. the glaserite for obtaining carnallite, epsom salt and step A is by 1：3.19～3.58：3.93～4.50 quality
Ratio is added in picromerite mother liquor, the stirring reaction at 15 DEG C～25 DEG C, and separation of solid and liquid obtains picromerite product after reaction；
The picromerite mother liquor is to have obtained mother liquor after separation of solid and liquid in picromerite saturated aqueous solution or step B.
2. method according to claim 1, it is characterised in that in step A, potassium chloride and sal glauberi and the quality of water
Than for 1：2.45～2.59：0.59～0.68.
3. method according to claim 1, it is characterised in that the reaction time in step A is 0.5～5 hour, in step B
Reaction time be 0.5～5 hour.
4. method according to claim 3, it is characterised in that the reaction time in step A is 1～3 hour, in step B
Reaction time is 1～3 hour.
5. method according to claim 1, it is characterised in that the sal glauberi is anhydrous by sulfur acid sodium more than 70%
Saltcake and water in mass ratio 1：After 1.5～2.5 Hybrid Heatings, separate out Jing after sedimentation filtration, natural cooling crystallization.
6. method according to claim 5, it is characterised in that the thenardite of sulfur acid sodium more than 95% and the mass ratio of water
For 1：2, heating-up temperature is 33 DEG C～50 DEG C.
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| CN1076435A (en) * | 1992-03-13 | 1993-09-22 | 化学工业部化学矿产地质研究院 | Saltpan method is produced schoenite and vitriolate of tartar |
| CN1065213C (en) * | 1998-05-21 | 2001-05-02 | 中国科学院青海盐湖研究所 | Process for preparing soft leonite |
| RU2350564C2 (en) * | 2007-05-04 | 2009-03-27 | Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук | Potassium alum production method |
| CN104030318B (en) * | 2014-07-01 | 2016-11-09 | 陈兆华 | Method with light halogen potassium chloride made of stones and picromerite |
| CN104261940B (en) * | 2014-09-24 | 2016-08-24 | 中国科学院青海盐湖研究所 | A kind of preparation method of potassic-magnesian fertilizer |
| CN104311164A (en) * | 2014-10-09 | 2015-01-28 | 龙蟒大地农业有限公司 | Production method of potash magnesium sulfate fertilizer |
| CN104529562A (en) * | 2014-11-20 | 2015-04-22 | 国投新疆罗布泊钾盐有限责任公司 | Method used for preparing potash magnesium sulphate fertilizer and potassium chloride fertilizer from carnallite |
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