CN1075041C - CO-production of potassium sulfate and sodium sulfate - Google Patents
CO-production of potassium sulfate and sodium sulfate Download PDFInfo
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- CN1075041C CN1075041C CN96110603A CN96110603A CN1075041C CN 1075041 C CN1075041 C CN 1075041C CN 96110603 A CN96110603 A CN 96110603A CN 96110603 A CN96110603 A CN 96110603A CN 1075041 C CN1075041 C CN 1075041C
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- sodium sulfate
- sodium
- mother liquor
- sulfate
- saltcake
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Abstract
The present invention relates to a method for producing potassium sulfate, or potassium sulfate and sodium sulfate by potassium salts and sodium sulfate/a water source, which comprises the following steps: (a). a sodium sulfate source and potassium salts are converted in a water medium to generate aphthitalite precipitates and first mother solution; (b). the potassium salt and water convert the aphthitalite precipitates to generate potassium sulfate precipitates and second mother solution; (c). the second mother solution is returned to the step (a); (d). the first mother solution is evaporated to separate out solid mixtures of sodium chloride and anhydrous sodium sulfate; (e). the solid mixtures of sodium chloride and anhydrous sodium sulfate can generate pure anhydrous sodium sulfate by the treatment of sodium sulfate/a water source; (f). the mother solution is recovered and is converted into potassium salts.
Description
The present invention relates to produce the method for vitriolate of tartar and sodium sulfate, more particularly, relate to the method for producing vitriolate of tartar and sodium sulfate with sylvite and hydration sodium sulfate.
The production of sodium sulfate:
Known have several different methods to produce sodium sulfate with the hydrate of sodium sulfate.Usually with saltcake (Na
2SO
410H
2O) produce high quality industrial sulphuric acid sodium.Natural saltcake ore deposit (" saltcake ") is present under the cold weather.Cool off natural salt solution (a kind of solution that obtains by solution mining, or produce and flow) and also can obtain saltcake, in groove or in the crystallizer (surface-cooled or vacuum cooling), carry out this cooling with liquid.
With saltcake production anhydrous sodium sulphate, generally be in multieffect evaporator or mechanical vapour recompression (MVR) vaporizer, to use the evaporative crystallization method, or in rotatory drier, carry out, or the fusing back is by carrying out with the sodium-chlor method of saltouing with evaporation.Saltcake often contains the unacceptable insolubles of high quality anhydrous sodium sulphate, and therefore, in order to obtain such material, dissolving, filtration (as auxiliary separation methods such as desliming) and evaporative crystallization operation all are necessary.In addition, can melt saltcake and produce low-quality " salt-cake " level sodium sulfate.Filter then and evaporate saturated mother liquor and produce high quality sodium sulfate.
The production of vitriolate of tartar:
Producing in the process of vitriolate of tartar with sylvite and sodium sulfate, the constraint requirements of thermodynamics and economic aspect is produced vitriolate of tartar with two stages.In traditional method, these stages comprise:
1) use sodium sulfate, the sylvite and the solution in stage 2 are produced glaserite (K
3Na (SO
4)
2);
2) use sylvite, the water and the glaserite in stage 1 are produced vitriolate of tartar.
The mother liquor of producing in the stage 1 contains a large amount of dissolved potassium and vitriol, generally needs to reclaim.Present known method is different from this programme that is used to reclaim these potassium and vitriol.
Several method (" Class1 ") has utilized Repone K, and sodium-chlor is with the different dissolving poweies of sodium sulfate/saltcake under high temperature and low temperature.Effluent (under 25 ℃) (seeing Fig. 1 b) from stage 1 effusive consisting of ' a ' is cooled to about 0 ℃, separates out the saltcake that will re-use, may also contain sodium-chlor, this depends on the balance of water in the system.The amount of potassium concentrates in liquid phase.After the separation, at high temperature evaporating solns produces the potassium ion in sodium-chlor and the further concentrated solution.Remove the sodium-chlor as byproduct, cooling heat solution is separated out the potassium as KCl and/or glaserite, and solution returns step of reaction more then.In addition, hot salt brine produces glaserite suspension with the saltcake reaction of reclaiming from the crystallisation by cooling stage, returns the stage 1 again.
Other working cycle (" type II ") utilize sodium-chlor and the Repone K difference of dissolving power at high temperature.Determine to join the water yield of step of reaction, make to produce glaserite and solution in the stage 1 (Fig. 1 b) ' b ' (25 ℃).The reaction of glaserite and sylvite and water generates potassium product and composition then ' solution of c '.This solution turns back to the stage 1.The effluent liquid in stage 1 at high temperature (75-110 ℃) evaporation produces pure NaCl, and final solution turns back to the stage 1.
Can go on the market even it must be emphasized that the sodium-chlor byproduct, producing vitriolate of tartar with sylvite and sodium sulfate also is low value-added method, above-mentioned multi-stage method be intensive capital and be energy-intensive.
The method of type I is complicated especially, requires a large amount of unit operations.Comprise 4 to 6 filtration steps, also do not comprise the filtration of washing potassium product.In addition, make the temperature of the effluent of Phase I reach 0 ℃ with crystallisation by cooling.The huge heat of crystallization (18.4kcal/M) of saltcake also must be got rid of at low temperature.Follow the cooling in this stage and heating expense to add that expensive equipment (crystallizer, heat exchanger, cooling system, etc.) is its important disadvantages.
The method of type II is not lower than the cooling stages of room temperature condition.Yet this method has the very large circulating fluid flow rate (K of～10 tons of/ton productions
2SO
4), this has increased energy expenditure.At evaporative crystallization in the stage, the water of evaporation has reduced the density of natural slip sharp to the low ratio of turnout, requires bigger crystallizer and/or more complicated crystallization processes.
Though saltcake is a kind of quite cheap sodium sulfate source, unnecessary water has reduced the conversion of step of reaction in the saltcake, and has increased the sulphate component of the effluent of stage I.Some circulation means can not be operated with saltcake, and other method needs additional unit operation (for example, evaporation).Up to the present, in the industrial method that does not also realize using saltcake.
Another kind of cheap sodium sulfate source is a hydration sodium sulfate.But water at the water of the saltcake ratio height to sodium sulfate, makes the problem of unnecessary water more worsen the ratio of sodium sulfate in hydration sodium sulfate.The circulation means of raw material does not also appear doing with hydration sodium sulfate at present.
Therefore, generally believing needs a kind of method of producing vitriolate of tartar with sodium sulfate, and it will be favourable that such method is arranged, and this method will be more efficient and more economical than present known method.
According to the present invention, a kind of method of producing vitriolate of tartar or vitriolate of tartar and sodium sulfate with sylvite and sodium sulfate/water source is provided, may further comprise the steps: (a) make sodium sulfate in water-bearing media, transform generation glaserite precipitation and first kind of mother liquor with sylvite; (b) glaserite and sylvite and water are transformed and form vitriolate of tartar precipitation and second kind of mother liquor; (c) make second kind of mother liquor return step (a); (d) first kind of mother liquor of evaporation separated out sodium-chlor and anhydrous sodium sulphate solid mixture in the third mother liquor; (e) make sodium-chlor and anhydrous sodium sulphate solid mixture produce pure anhydrous sodium sulphate through Sodium Persulfate/water treatment; (f) reclaim the third mother liquor and be used to change into sylvite.
According to the other characteristics in the following embodiment preferred of the present invention, the sodium sulfate source is a saltcake, sulfate hemihydrate sodium, the i.e. mixture of sodium sulfate and saltcake or part aquation sodium sulfate, or in the presence of sodium-chlor, can produce any metabisulfite solution of sodium sulfate, as sodium magnesium rock solution.
The present invention allows to use the sodium sulfate source that cheaply can get.Utilization of the present invention varies with temperature the greatest differences of the solubleness of the solubleness of Repone K and sodium-chlor and sodium sulfate.Raise with temperature, the solubleness increase of Repone K is very big, and the solubleness of sodium-chlor has only small increase, and the solubleness of sodium sulfate reduces or keeps constant.
The solubleness that the present invention also utilizes sodium sulfate increases the fact that reduces with the concentration of sodium-chlor.Therefore, at high temperature the sodium-chlor of Sheng Chaning/sodium sulfate solid mixture can be added in the sodium sulfate feed source, and sodium-chlor is dissolved fully.The solubleness that this has reduced sodium sulfate makes anhydrous sodium sulphate separate out from solution as unique stable solid phase.Therefore, raw material is converted into anhydrous sodium sulphate, and from evaporation stage reclaim(ed) sulfuric acid sodium.This sodium sulfate can be used to produce vitriolate of tartar, and any unnecessary material all is valuable byproduct.
This paper describes the present invention by example with reference to the accompanying drawings, wherein:
Fig. 1 a, 1b and 1c are respectively Na
2SO
4/ 2NaCl/K
2SO
4/ 2KCl/H
2The O system is at 0 ℃, the solution phasor of 25 ℃ and 100 ℃;
Fig. 2 is the skeleton diagram that the method according to this invention is described in signal.
The present invention is the method for co-production vitriolate of tartar and sodium sulfate.Can understand the principle and the operation of the method according to this invention better referring to accompanying drawing and explanation thereof.
Referring now to accompanying drawing,, Fig. 2 has shown several embodiments of the present invention.
The method that proposes realizes according to the following procedure: carry out sylvite 10 and sodium sulfate 46 and/or 76 conversions to vitriolate of tartar 42 two step of reaction.In the fs, or in the glaserite production phase 14, react at 15-100 ℃.But when reaction kinetics and crystalline growth speed raise when improving with temperature, equilibrium criterion shows that conversion raises with temperature and reduces, and the energy expenditure increase.Therefore (20-40 ℃) operation is best under the condition near room temperature.
The sylvite 10 that introduction comes from recovery stage, sodium sulfate 46 and/or 76, liquid stream 28 and the salt solution 40 that comes at the glaserite catabolic phase.The sodium sulfate source is anhydrous sodium sulphate basically or just, but can add some saltcake or hydration sodium sulfate (not shown).Term ' sylvite ' mean any material that contains Repone K of expression, for example comprise sylvine.
In the fs 14, sodium sulfate and sylvite dissolving produce the supersaturation with respect to glaserite, and glaserite is separated out.System also can separate out some sodium-chlor with respect to the sodium-chlor supersaturation simultaneously.Slurry dewatering also transmits 20 to glaserite catabolic phase 16.Mother liquor 26 is by following the composition (wt%): potassium: 2.5-6; Sodium: 7.5-10; Muriate: 10-17; Vitriol: 1.3-8; Water: surplus.The composition of mother liquor is equivalent at the point on the NaCl/ glaserite line of balance and more than the NaCl/ glaserite line of balance or at Na
2SO
4On/glaserite the line of balance and/or Na
2SO
4The point on/glaserite line of balance right side.The mother liquor that contains a large amount of potassium and vitriol is in following recovery stage processing.
Glaserite catabolic phase 16 carries out at 15-60 ℃, because described same consideration of fs, preferred temperature range is 20-40 ℃.Sylvite 10 and water 18 and liquid stream 20 introducing together that obtains in the fs 14.Sylvite and the dissolving of glaserite solid produce a supersaturation with respect to vitriolate of tartar, make vitriolate of tartar select to separate out.When mother liquor near KCl/K
2SO
4During the no variable point of/glaserite/water, obtain maximum conversion.52 dehydrations of vitriolate of tartar slip also wash 22, then the product 42 of dry wet.The mother liquor of getting rid of from glaserite catabolic phase 16 40 turns back to the glaserite generation stage 14; But the washing water of consumption can use at glaserite catabolic phase 16.Stage 14,16,22, some or all can in a single adverse current jump mixing tank, carry out.
The salt solution 26 that produce in the glaserite production phase 70-130 ℃ of evaporation 60 remove and anhydrate 62, and preferred temperature range is 95-110 ℃.If desired, can before evaporation, filter this salt solution (not shown) to remove any insolubles.Evaporation of water has produced the supersaturation (this depends on service temperature, the water yield that the feed brinish is formed and unit feed amount is evaporated for sodium sulfate, sodium-chlor, or the two supersaturation simultaneously) of sodium salt.Must be noted that not excessive evaporation.During excessive evaporation, the mistake of sodium salt analyzes and makes the composition of mother liquor shift to NaCl/Na
2SO
4The no variable point of/glaserite/water produces separating out jointly of undesirable glaserite at this point.
After solid/liquid separation, cool off 70 rich sylvite water 28 and make it return glaserite catabolic phase 14.The sodium salt 30 that in evaporation and crystal process, produces in suitable containers through low-quality and/or aqueous sulfuric acid sodium source 12 (as hydration sodium sulfate, saltcake, vanthoffite, or similar material) handle, and be necessary to add entry.Above-mentioned each, no matter independent or put together, after this individually or be referred to as " sodium sulfate/water source ".Sodium-chlor and white sodium magnesium rock reaction can easily obtain vanthoffite.
In order to obtain high-quality anhydrous sodium sulphate product, can filter aqueous sodium sulfate source, remove insoluble impurity.The crystalline saltcake does not generally contain such impurity from the salt solution of cleaning, can directly add 33 in container 72.In addition, can melt the saltcake 35 that contains impurity in suitable melting tank 34, filtration contains water 74 before being incorporated into liquid stream 30, produces glaserite with spissated solid 76 in first step of reaction.The another kind of selection is directly to add solid phase 76 all or part in filtration washing container 82.
The solid sodium chloride that comes from liquid stream 30 is not in balance in rich sulfate medium, and dissolving.Dissolved sodium-chlor has reduced the solubleness of sodium sulfate, and sodium sulfate is separated out.Filtration and water or clean metabisulfite solution 56 thoroughly wash 82 sodium sulfate slips 44 with the adverse current form, and the low sulfuric chlorohydrin sodium product 84 of acquisition is dry then.The washing lotion 86 that consumes is sent into container 72.Discharge is from the effluent liquid 80 that container 72 comes out, and wherein contains the following vitriol of 20mol%, uses in another process, or is used for processing high quality sodium-chlor and sodium sulfate.
More than describe the present invention, but also can make variation, revise and the present invention is made other application the present invention with limited embodiment.
Claims (11)
1. with the method for Repone K and sodium sulfate/water source production vitriolate of tartar and sodium sulfate, may further comprise the steps:
(a) the sodium sulfate source is transformed in water medium with Repone K, produce glaserite precipitation and first kind of mother liquor;
(b) transform said glaserite precipitation with Repone K and water and produce vitriolate of tartar precipitation and second kind of mother liquor;
(c) return said second kind of mother liquor to step (a);
(d) the said first kind of mother liquor of evaporation makes precipitated sodium chloride and anhydrous sodium sulphate solid mixture in the third mother liquor;
(e) make said sodium-chlor and anhydrous sodium sulphate solid mixture produce pure anhydrous sodium sulphate through the processing at Sodium Persulfate/water source;
(f) reclaim said the third mother liquor and be used to be converted into Repone K.
2. according to the method for claim 1, also comprise:
(g) the said anhydrous sodium sulphate of necessary amount is turned back to step (a) as raw material, and remove any unnecessary material as byproduct.
3. according to the process of claim 1 wherein that said sodium sulfate/water source comprises hydration sodium sulfate.
4. according to the process of claim 1 wherein that said sodium sulfate/water source comprises saltcake.
5. according to the process of claim 1 wherein that said sodium sulfate/water source comprises sulfate hemihydrate sodium.
6. according to the process of claim 1 wherein that said sodium sulfate/water source comprises vanthoffite.
7. obtain aqueous sodium persulfate solution according to the process of claim 1 wherein by fusing saltcake or half anhydrous sodium sulphate, the solid sodium sulfate that produces in melting tank is as the raw material of step (a).
8. obtain aqueous sodium persulfate solution according to the process of claim 1 wherein by the fusing saltcake, the solid of removing generation is used as the raw material of step (a) as byproduct from the solid sodium sulfate of aqueous sodium persulfate solution production.
9. according to the process of claim 1 wherein that at least a sodium sulfate source that is used in the step (a) is low-quality salt-cake, make the high quality sodium sulfate that has at least a part to produce can be used as byproduct and remove.
10. according to the process of claim 1 wherein that said the third mother liquor and saltcake transform, reaction mixture, glaserite is separated out in the 4th kind of mother liquor, and is recovered to step (a), then according to the 4th kind of mother liquor of step (d) evaporation.
11. method according to claim 1, the saltcake of wherein said the third mother liquor and interpolation carries out converted in-situ in step (a), glaserite is separated out in said first kind of mother liquor, and be recovered to step (b), then according to first kind of mother liquor of step (d) evaporation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96110603A CN1075041C (en) | 1996-06-19 | 1996-06-19 | CO-production of potassium sulfate and sodium sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96110603A CN1075041C (en) | 1996-06-19 | 1996-06-19 | CO-production of potassium sulfate and sodium sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1168861A CN1168861A (en) | 1997-12-31 |
| CN1075041C true CN1075041C (en) | 2001-11-21 |
Family
ID=5120879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96110603A Expired - Lifetime CN1075041C (en) | 1996-06-19 | 1996-06-19 | CO-production of potassium sulfate and sodium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1075041C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071707C (en) * | 1998-04-20 | 2001-09-26 | 邓绍齐 | Technological process of preparing potassium sulfate with chromium containing sodium sulfate |
| CN107902677A (en) | 2016-12-12 | 2018-04-13 | 威立雅水处理技术公司 | The method that potassium sulfate and sodium chloride are produced from waste water |
| CN115246650A (en) * | 2021-08-09 | 2022-10-28 | 江苏美东环境科技有限公司 | Method for preparing industrial potassium sulfate from hazardous organic waste salt containing potassium chloride and sodium sulfate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080617A (en) * | 1992-07-02 | 1994-01-12 | 化学工业部上海化工研究院 | The manufacture method of vitriolate of tartar |
| CN1084492A (en) * | 1992-09-12 | 1994-03-30 | 国家海洋局天津海水淡化与综合利用研究所 | Bittern and Repone K prepare the method for vitriolate of tartar |
-
1996
- 1996-06-19 CN CN96110603A patent/CN1075041C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080617A (en) * | 1992-07-02 | 1994-01-12 | 化学工业部上海化工研究院 | The manufacture method of vitriolate of tartar |
| CN1084492A (en) * | 1992-09-12 | 1994-03-30 | 国家海洋局天津海水淡化与综合利用研究所 | Bittern and Repone K prepare the method for vitriolate of tartar |
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| Publication number | Publication date |
|---|---|
| CN1168861A (en) | 1997-12-31 |
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