CN1125776C - Metathesis process for producing potassium sulfate in ammonia/water medium - Google Patents
Metathesis process for producing potassium sulfate in ammonia/water medium Download PDFInfo
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- CN1125776C CN1125776C CN99112051A CN99112051A CN1125776C CN 1125776 C CN1125776 C CN 1125776C CN 99112051 A CN99112051 A CN 99112051A CN 99112051 A CN99112051 A CN 99112051A CN 1125776 C CN1125776 C CN 1125776C
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- ammonia
- sulfate
- potassium
- potassium sulfate
- tartar
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Abstract
The present invention relates to a new method for preparing potassium sulfate by double decomposition in an ammonia/aqueous medium. Firstly, mixed materials in which potassium ions and sulfate radical ions are contained are prepared in a converter, ammonia gas is led in at the time of continuous stirring; then, the solid-liquid separation is carried out to the system, and the product of potassium sulfate can be obtained by washing and drying a filter cake; mother solution in which ammonia and a byproduct are recovered can be cyclically used; if the filter cake is aphthitalite, potassium sulfate is prepared by further conversion. More than 50% of K2O and less than 1% of Cl<-> are contained in a potassium sulfate product. Compared with the potassium sulfate production technology by the double decomposition method, the present invention has the advantages of high one-time conversion rate of raw materials, few cyclic materials, etc.; accordingly, the purposes of energy saving and cost reduction can be achieved.
Description
The method of vitriolate of tartar is produced in metathesis in a kind of ammonia/water medium.
The invention belongs to field of inorganic chemical engineering, more particularly is to be the production method that vitriolate of tartar is produced in the raw material metathesis to contain potassium ion and sulfate ion in ammonia/water medium.
Before the present invention, nearly 5,000,000 tons of world's vitriolate of tartar overall throughput, about 20% from the producing potassium salt ore, comprises sal epsom alum type kieserohalosylvite, anhydrokainite, kainite etc.; Nearly 70% conversion from Repone K and sulfuric acid and various vitriol etc.; All the other are then from seawater, salt lake brine and other resource.Its working method has substantially: 1. ore processing method: this method mainly is sent in the development and use of puritan filler potassium ore resources; 2. Repone K and vitriolic conversion method: wherein, mannheim (Mannheim) method is by metering Repone K and sulfuric acid at high temperature to be reacted to generate vitriolate of tartar and hydrogenchloride, this method facility investment greatly, seriously corroded; The sulfurous gas method is with burning sulphur or contains that sulfur mineral obtains sulfurous gas, water vapour and excess air feeds reaction chamber and Repone K reaction, makes it transform generation vitriolate of tartar and hydrogenchloride; Forming the method for putting, is to utilize organic solvent to HCl and H
2SO
4The character that avidity is different and obtain sulphur and change potassium, used association agent costs an arm and a leg, the product cost height; 3. Repone K and vitriol double decomposition: wherein, the gypsum method is that vitriolate of tartar is produced in metathesis in ammonia/aqueous solution with gypsum and Repone K; Mirabilite method is at first to make sodium sulfate and Repone K reaction generate glaserite, and glaserite reacts with Repone K and separates out vitriolate of tartar then, and shortcoming is that the separation of potassium sodium is not thorough, the energy consumption height; The ammonium sulfate method is that ammonium sulfate and Repone K are changed into vitriolate of tartar and ammonium chloride in the aqueous solution under 50 ℃, and technology is simple, but product purity is poor, and the potassium utilization ratio is low.Because China's vitriol reserves are abundant, Repone K and vitriol double decomposition are the main method that China's vitriolate of tartar is produced.In addition, also has ion exchange method manufacture vitriolate of tartar etc.
The objective of the invention is to overcome that the deficiency of technology is produced in existing metathesis and the cover novel process scheme that proposes, provide a kind of in nitrogen/water medium metathesis produce the method for vitriolate of tartar.
Technical essential of the present invention realizes by following technical measures.The present invention is to be the method that raw material is produced vitriolate of tartar with potassium ion and sulfate ion in ammonia/water medium, it is characterized in that being undertaken by following step:
(1) in convertor the preparation potassium concentration at 0.2～5mol/L and sulfate ion concentration mixture at 0.1～6mol/L,
(2) feed ammonia when constantly stirring, ammonia concentration is between 1-30mol/L in the liquid phase during reaction terminating, and temperature is at-10～50 ℃, and transformation time is 0.5-6 hour,
(3) above-mentioned system of closing the solid-liquid coexistence of ammonia is carried out solid-liquid separation, filter cake is through washing, be drying to obtain product, mother liquor recycle after reclaiming ammonia and byproduct; Filter cake is glaserite in this way, must further transform with Repone K and produce vitriolate of tartar.
Potassium ion in the above-mentioned steps (1) is meant that Repone K (comprises other water-soluble potassium-bearing minerals, together following) or natural salt water (salt lake saline, subsurface brine and salt pan bittern etc., potassium ion down together), sulfate ion is meant the sulfate ion in sodium sulfate or ammonium sulfate or sulfuric acid or the natural salt water; Reaction terminating temperature in the step (2) is good with 0～30 ℃, and ammonia concentration is good with 5-15mol/L.
Embodiments of the invention:
Example 1 potassium chloride 1050g, ammonium sulfate 930g (KCl/ (HH
4)
2SO
4=2: 1, mol ratio), water 5000ml under the normal temperature, feeds ammonia when constantly stirring in convertor.Reacting back liquid phase ammonia concentration is 14.49mol/L, density p=0.9172, and temperature is 26 ℃ eventually, and through separation, the dry vitriolate of tartar 1270g that gets, transformation efficiency of sulfate radical is 98%, K in the product
2O＞50%, Cl
-＜1%.
Example 2 potassium chloride 800g, sodium sulfate 1000g (KCl/Na
2SO
4=1.5: 1, mol ratio) and water 5000ml in convertor, under the room temperature, when constantly stirring, feed ammonia.Reaction back liquid phase ammonia concentration is 13.14mol/L, density p=0.9227, temperature is 28 ℃ eventually, through separate product 1265g, wherein contain glaserite 92.1%, transformation efficiency of sulfate radical is 94%, and then glaserite reacts with Repone K and produces vitriolate of tartar, K in the product
2O＞50%, Cl
-＜1%.
Example 3 is got salt pan bittern de-magging mother liquor and (is contained Mg0.2954mol/L, Cl
-5.544mol/L, SO
4 2-0.633mol/L, NH
4 +3.05mol/L, K
+0.380mol/L) 5000ml and KCl 211g (K
+/ SO
4 2-=1.5: 1, mol ratio) in convertor; Under the room temperature, when constantly stirring, feed ammonia.Reaction back liquid phase ammonia concentration is 12.24mol/L, density p=1.007, temperature is 27 ℃ eventually, through separate product 551g, wherein contain glaserite 91.1%, transformation efficiency of sulfate radical is 95.5%, and then glaserite reacts with Repone K and produces vitriolate of tartar, K in the product
2O＞50%, Cl
-＜1%.
It is 98% vitriol oil 750ml, Repone K 2024g (KCl/H that example 4 is got concentration
2SO
4=2: 1, mol ratio) and water 4120ml in convertor; Under the room temperature, when constantly stirring, feed ammonia.Reacting back liquid phase ammonia concentration is 12.07mol/L, density p=0.9588, and temperature is 28 ℃ eventually, and through separation, the dry product 2200g that gets, transformation efficiency of potassium is 93%.K in the product
2O＞50%, Cl
-＜1%.
Compared with the prior art the present invention has following advantage: the disposable conversion ratio of prior art sulfate radical Be generally 60-70%, the disposable conversion ratio height of raw materials technology of the present invention can reach 90%-98%; Existing Potassium product circulated material quantity per ton is at the 5-20 cubic meter in the technology production process, and the present invention's sulfuric acid per ton Potassium product recycle stock is the 0.5-2 cubic meter only, and recycle stock is few, and energy savings reduces cost greatly.
Claims (1)
- One kind in ammonia/water medium metathesis produce the method for vitriolate of tartar, it is to be the method that raw material is produced vitriolate of tartar with potassium ion and sulfate ion in ammonia/water medium, it is characterized in that being undertaken by following step:(1) in convertor the preparation potassium concentration at 0.2-5mol/L and sulfate ion concentration mixture at 0.1～6mol/L,(2) feed ammonia when constantly stirring, ammonia concentration is between 1-30mol/L in the liquid phase during reaction terminating, and temperature is at-10-50 ℃, and transformation time is 0.5-6 hour,(3) above-mentioned ammoniated solid-liquid coexistence system is carried out solid-liquid separation, filter cake is through washing, be drying to obtain product, and mother liquor recycle after reclaiming ammonia and byproduct: filter cake is glaserite in this way, must further transform and produce vitriolate of tartar.Potassium ion in the above-mentioned steps (1) is meant the potassium ion in natural salt water, salt lake saline, subsurface brine and the salt pan bittern, and sulfate ion is meant the sulfate ion in sodium sulfate or ammonium sulfate or sulfuric acid or the natural salt water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112051A CN1125776C (en) | 1999-01-27 | 1999-01-27 | Metathesis process for producing potassium sulfate in ammonia/water medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112051A CN1125776C (en) | 1999-01-27 | 1999-01-27 | Metathesis process for producing potassium sulfate in ammonia/water medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1227188A CN1227188A (en) | 1999-09-01 |
| CN1125776C true CN1125776C (en) | 2003-10-29 |
Family
ID=5275392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99112051A Expired - Fee Related CN1125776C (en) | 1999-01-27 | 1999-01-27 | Metathesis process for producing potassium sulfate in ammonia/water medium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1125776C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034906A (en) * | 1988-02-11 | 1989-08-23 | 沈阳化工综合利用研究所 | A kind of method of producing vitriolate of tartar |
| CN1082001A (en) * | 1993-04-23 | 1994-02-16 | 陕西省石油化工研究设计院 | The preparation vitriolate of tartar in and synthesis method |
-
1999
- 1999-01-27 CN CN99112051A patent/CN1125776C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034906A (en) * | 1988-02-11 | 1989-08-23 | 沈阳化工综合利用研究所 | A kind of method of producing vitriolate of tartar |
| CN1082001A (en) * | 1993-04-23 | 1994-02-16 | 陕西省石油化工研究设计院 | The preparation vitriolate of tartar in and synthesis method |
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| Publication number | Publication date |
|---|---|
| CN1227188A (en) | 1999-09-01 |
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