CN1041619C - Process for producing potassium sulfate by plaster stone conversion method - Google Patents
Process for producing potassium sulfate by plaster stone conversion method Download PDFInfo
- Publication number
- CN1041619C CN1041619C CN95100596A CN95100596A CN1041619C CN 1041619 C CN1041619 C CN 1041619C CN 95100596 A CN95100596 A CN 95100596A CN 95100596 A CN95100596 A CN 95100596A CN 1041619 C CN1041619 C CN 1041619C
- Authority
- CN
- China
- Prior art keywords
- potassium sulfate
- filtrate
- gypsum
- water
- ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 229910052939 potassium sulfate Inorganic materials 0.000 title claims abstract description 25
- 235000011151 potassium sulphates Nutrition 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 16
- 239000011505 plaster Substances 0.000 title 1
- 239000004575 stone Substances 0.000 title 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000010440 gypsum Substances 0.000 claims abstract description 22
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 22
- 239000001103 potassium chloride Substances 0.000 claims abstract description 11
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 12
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002686 phosphate fertilizer Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910017917 NH4 Cl Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Fertilizers (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a technology for preparing potassium sulfate with a gypsum conversion method, which comprises the following steps that the gypsum is processed at a certain temperature and converted into a soluble salt; then potassium chloride is added according to a certain proportion, the mixture is heated for a double decomposition reaction so as to obtain the potassium sulfate, and then filter liquor is evaporated to obtain ammonium chloride. The present invention can directly use gypsum as raw material for preparing potassium sulfate after the gypsum is converted, utilize gypsum ore whose applicable values are not high in all parts of the country, and the by-products of phosphogypsum in the phosphate fertilizer industry, and have the characteristics of low cost, less investment, short production period, etc.
Description
The present invention relates to a process for producing potassium sulfate by using gypsum conversion method.
The existing chemical method for producing potassium sulfate needs soluble sulfate or the reaction of sulfuric acid and potassium chloride, and the Mannheim method using sulfuric acid has high-temperature reaction, serious corrosion and stable byproduct hydrochloric acid users. Other methods, such as the mirabilite method and the ammonium sulfate method, have the problems of difficulty in treatment of the sodium chloride produced as a by-product and high production cost. The new process for producing potassium sulfate and ammonium chloride by phosphogypsum conversion method proposed by Chinese patent 1095055A is characterized by that it adopts phosphogypsum to refine so as to obtain wet-base refined gypsum, then fully mixes it with ammonium hydrogen carbonate, then adds ammonia material to make negative pressure reaction, and makes the ammonia sulfate filtrate undergo the processes of filtration and separation so as to obtain ammonium sulfate filtrate, and makes the pH value be regulated, concentrated, crystallized and dried so as to obtain the potassium sulfate.
The invention aims to solve the problems, and aims to provide a process for producing potassium sulfate by using gypsum and phosphogypsum as raw materials, which has the advantages of low investment and simple process.
The present invention directly uses gypsum as raw material, and can utilize gypsum ore with small application in various places and utilize by-product phosphogypsum of phosphate fertilizer industry, and has the characteristics of low cost, small investment and short production period.
The present invention uses ammonia water and ammonium hydrogen carbonate to treat gypsum at a certain temp. to convert it into soluble salt, then adds potassium chloride according to a certain proportion and heats it to make double decomposition reaction to obtain potassium sulfate, and evaporates the filtrate to obtain dry water portion so as to obtain ammonium chloride.
FIG. 1 is a process flow diagram of the present invention.
The present invention will now be described in detail with reference to the figures.
The principle of the invention is that the gypsum is less dissolved in water and can not be directly used for preparing potassium sulfate, ammonia water and ammonium bicarbonate are firstly used for processing, and the reaction formula is as follows:
dissolving ammonium bicarbonate with ammonia water in calculated amount to obtain ammonium carbonate, diluting with water by 2-5 times, stirring at 10-35 deg.C to completely dissolve, adding gypsum powder of 100-300 meshes in calculated amount of 1-1.5 times, reacting for 1-2 times to obtain ammonium sulfate and calcium carbonate as by-product, sampling, checking, filtering to obtain filtrate without carbonate radical, washing the residue with small amount of water for 1-3 times, mixing the washing water and the filtrate, sampling, analyzing the ammonium sulfate content in the filtrate, placing the filtrate in a reactor, heating to 50-100 deg.C, adding KCl in amount of 0.7-1 times in calculated amount while stirring according to the ammonium sulfate content in the filtrate, reacting for 0.5-3 hr to separate out potassium sulfate crystals, evaporating a part of the filtrate without complete separation of water to separate out residual potassium sulfate, cooling and filtering, washing with a small amount of water, drying to obtain high-content potassium sulfate crystals, and evaporating the filtrate to dryness to obtain ammonium chloride. The ammonium sulfate solution subjected to the double decomposition reaction with potassium chloride is obtained by treating gypsum with an ammonium carbonate solution. The calcium carbonate as by-product can be used as diluent for producing 50% potassium sulfate.
Example 1: 1000 g of agricultural first-grade product NH4HCO3 and 1000ml of 24% industrial ammonia water are taken, 2000ml of water is added for dissolving, the temperature is controlled at 30 ℃, 2300 g of construction gypsum powder (CaSO4 and # 6290%) is added under stirring, the reaction lasts for 1 hour, the mixture is filtered, washed by 2500ml of water for four times, filtered again, the washing water and the filtrate are combined to obtain 5100 g of filtrate, the content of (NH4)2SO4 is 29%, the content of (NH4)2SO4 is reduced to 1470 g, KCl1700 g and the content of the KCl # 6298% are added, the mixture is heated to boil, kept for 5 minutes, naturally cooled to 20 ℃, filtered after half an hour, washed by 500ml of water once and dried to obtain 1750 g of potassium sulfate, the yield of the # 6290% (calculated by potassium chloride), and the water content of the filtrate is evaporated to obtain 1400 g of NH4 Cl.
Example 2: 31000 g of agricultural first-grade product NH4HCO, 1700 g of KCl and 1000ml of 24% ammonia water are taken, 4500ml of water is added, NH4HCO3, KCl and ammonia water are mixed and dissolved, the temperature is kept at 25 ℃, 2650 g of gypsum powder is added for many times after complete stirring and dissolution, the reaction is carried out for 1.5 hours, the reaction is complete when no carbonate ions exist in filtrate, the filtrate is filtered, washed once with 500ml of water, dried and crushed to obtain 3200 g of 50% potassium sulfate (actual measurement value is 51.2%), and the filtrate is evaporated to dryness to obtain 1450 g of NH4 Cl.
The invention has the characteristics of short process flow, quick reaction, easy control, simple and convenient operation, less investment, less used equipment and no waste residue discharge, is favorable for protecting the environment, and is a technology with stronger applicability and easy popularization.
Claims (3)
1. A process for producing potassium sulfate by a gypsum conversion method is characterized by comprising the following steps: dissolving ammonium bicarbonate with ammonia water in calculated amount to obtain ammonium carbonate, diluting with water by 2-5 times, stirring at 10-35 deg.C to completely dissolve, adding gypsum powder of 100 meshes and 300 meshes in calculated amount of 1-1.5 times, reacting for 1-2 hr to obtain ammonium sulfate and calcium carbonate as by-product, sampling, checking, filtering to obtain filtrate without carbonate radical, washing the residue with small amount of water for 1-3 times, mixing the washing water and the filtrate, sampling, analyzing ammonium sulfate content in the filtrate, placing the filtrate in a reactor, heating to 50-100 deg.C, adding KCl in amount of 0.7-1 times in calculated amount while stirring according to ammonium sulfate content in the filtrate, reacting for 0.5-3 hr to obtain potassium sulfate crystal, evaporating a part of water from the filtrate to completely separate out residual potassium sulfate, cooling, filtering, washing with a small amount of water, drying to obtain high-content potassium sulfate crystals, and evaporating the filtrate to dryness to obtain ammonium chloride.
2. The process for the production of potassium sulfate by gypsum conversion as set forth in claim 1, wherein: the ammonium sulfate solution subjected to the double decomposition reaction with potassium chloride is obtained by treating gypsum with an ammonium carbonate solution.
3. The process for the production of potassium sulfate by gypsum conversion as set forth in claim 1, wherein: the by-product calcium carbonate can be used as diluent for producing 50% potassium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95100596A CN1041619C (en) | 1995-02-20 | 1995-02-20 | Process for producing potassium sulfate by plaster stone conversion method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95100596A CN1041619C (en) | 1995-02-20 | 1995-02-20 | Process for producing potassium sulfate by plaster stone conversion method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1114635A CN1114635A (en) | 1996-01-10 |
| CN1041619C true CN1041619C (en) | 1999-01-13 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95100596A Expired - Fee Related CN1041619C (en) | 1995-02-20 | 1995-02-20 | Process for producing potassium sulfate by plaster stone conversion method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1041619C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050819C (en) * | 1997-05-16 | 2000-03-29 | 重庆侨益物资站 | Technology for producing potassium sulfate using flue gas desulfating gypsum |
| WO2008062430A2 (en) * | 2006-08-25 | 2008-05-29 | Acc Limited | A method of inertising the impurities in phosphogypsum |
| CN102583443B (en) * | 2012-04-09 | 2014-05-07 | 瓮福（集团）有限责任公司 | Method for producing ammonium sulfate by using ammonium bicarbonate as main raw material |
| CN104016380B (en) * | 2014-06-19 | 2015-08-12 | 龙岩紫云化学科技有限公司 | A kind of gypsum prepares the method for potassium sulfate |
| CN108367934A (en) * | 2015-12-22 | 2018-08-03 | 雅拉达洛尔有限公司 | The method that control forms the compound of sulfate in high environment temperature prepares potassium sulfate from mine containing potassium |
| CN106587113A (en) * | 2016-11-30 | 2017-04-26 | 东至天孚化工有限公司 | Method for preparing potassium sulfate from phosphogypsum |
| CN111392746B (en) * | 2020-03-30 | 2021-10-08 | 中国科学院过程工程研究所 | Resource processing system and processing method for mixed salt solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089577A (en) * | 1993-12-30 | 1994-07-20 | 天津轻工业学院 | Ammoniation process is produced vitriolate of tartar |
| CN1095055A (en) * | 1993-05-08 | 1994-11-16 | 曾繁威 | Produce the novel process of vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method |
-
1995
- 1995-02-20 CN CN95100596A patent/CN1041619C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095055A (en) * | 1993-05-08 | 1994-11-16 | 曾繁威 | Produce the novel process of vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method |
| CN1089577A (en) * | 1993-12-30 | 1994-07-20 | 天津轻工业学院 | Ammoniation process is produced vitriolate of tartar |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1114635A (en) | 1996-01-10 |
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