CN101717099B - Method for preparing potassium sulfite by using sea water - Google Patents
Method for preparing potassium sulfite by using sea water Download PDFInfo
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- CN101717099B CN101717099B CN 200910310617 CN200910310617A CN101717099B CN 101717099 B CN101717099 B CN 101717099B CN 200910310617 CN200910310617 CN 200910310617 CN 200910310617 A CN200910310617 A CN 200910310617A CN 101717099 B CN101717099 B CN 101717099B
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- potassium
- sulfite
- ammonium
- seawater
- zeolite
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Abstract
The present invention relates to a method for preparing potassium sulfite by taking sea water, ammonium sulfite and potassium hydroxide as raw materials, and comprises the technical steps of: taking natural zeolite as inorganic ion adsorbing agent to absorb potassium ions inside the sea water; taking 100-150g/L of ammonium sulfite solution as eluant, eluting the potassium ionson the natural zeolite, and obtaining potassium-rich mother liquid containing potassium, ammonium and sulfate ions; according to the molar ratio between the ammonium sulfite and the potassium hydroxide in the solution as 1:2 adding the potassium hydroxide into the potassium-rich mother liquid, heating the potassium-rich mother liquid added with the potassium hydroxide at 80-90 DEG C for evaporating ammonium, and obtaining ammonium evaporation finished liquid; and finally, further evaporating and concentrating the ammonium evaporation finished liquid, evaporating to 105 DEG C, cooling, and obtaining potassium sulfite concentrated solution. The method for preparing potassium sulfite provided by the present invention opens up new potassium resource prepared by the sea water, and has the characteristics of wide source of materials and low production cost.
Description
Technical field
The present invention relates to the preparation technique of sylvite in the field of inorganic chemical engineering, particularly utilize seawater to produce the method for potassium sulfite for raw material.
Background technology
Potassium sulfite is a kind of broad-spectrum industrial chemicals, in photographic industry, as the reductive agent of developing solution; In foodstuffs industry,, be used for the fresh-keeping of fresh fruit of vegetables, meat as SYNTHETIC OPTICAL WHITNER, sanitas, oxidation inhibitor; In printing and dyeing industry, as the reductive agent of dyestuff; In addition, also can in processing wool and silk and pulping and paper-making, be used as SYNTHETIC OPTICAL WHITNER.
At present, produce potassium sulfite and mainly contain salt of wormwood method and potassium hydroxide method.
It is sulfurous gas to be fed solution of potassium carbonate react that the salt of wormwood legal system is got potassium sulfite technology, treats that the salt of wormwood that solution adds equivalent after saturated makes through evaporation, crystallization again.Its principal reaction formula is: SO
2+ K
2CO
3=K
2SO
3+ CO
2The potassium sulfite purity of this method preparation is relatively poor.
Potassium hydroxide method is to produce potassium sulfite by potassium hydroxide and sulfurous gas reaction.Its principal reaction formula is 2KOH+SO
2=K
2SO
3+ H
2O, this method can make purer potassium sulfite.
The potassium sulfite preparation method of above-mentioned prior art is produced by the second product of sylvite, and salt of wormwood is to be produced by the method or the potassium hydroxide carbonization of ion-exchange by Repone K, and potassium hydroxide is to be produced by the Repone K electrolysis.As the salt of wormwood of producing the potassium sulfite raw material and the production process complexity of potassium hydroxide, price is higher.Therefore, the potassium sulfite preparation method of prior art, ubiquity production cost problem of higher demands exploring new producing and manufacturing technique urgently.
Summary of the invention
At the problems referred to above that prior art exists, the present invention has released the method for utilizing seawater to produce potassium sulfite.This method is raw material with the seawater, adopts processing steps such as absorption, wash-out, steaming ammonium, evaporation concentration and cooling to produce the potassium sulfite concentrated solution.
The seawater that utilizes involved in the present invention is produced the method for potassium sulfite, and its processing step comprises: with the natural zeolite is the mineral ion sorbent material, the potassium ion in the adsorbing seawater; Be eluent with the ammonium sulfite solution again, the potassium ion on the natural zeolite is washed, obtain containing the rich potassium mother liquor of potassium, ammonium, sulfite ion; To add the rich potassium mother liquor heating ammonia still process of potassium hydroxide again, and make ammonia still process and finish liquid; The further evaporation concentration of liquid is finished in ammonia still process, and cooling makes the potassium sulfite concentrated solution then.
The natural zeolite of potassium ion is an inorganic ion exchanger in the adsorbing seawater, adsorbs to utilize after saturated sodium chloride solution to make its regeneration, and circulation is adsorbed, the ion exchange process of wash-out and zeolite regeneration.
The ion exchange process of absorption for convenience of description, wash-out and zeolite regeneration is represented silico-aluminate solid skeletal in the zeolite with Z, and then NaZ represents na-pretreated zeolite, and KZ represents potassium type zeolite, NH
4Z represents ammonium type zeolite.
Concrete processing step of the present invention and processing parameter make the following instructions.
(1) absorption
Seawater is fed the natural zeolite of sodium type, then potassium ion K in the seawater
+Be adsorbed on the zeolite, reach K
+With the purpose of other ion initial gross separation, na-pretreated zeolite becomes potassium type zeolite.
Seawater+NaZ → suction back seawater+KZ
In this processing step, seawater is the clarifying natural sea-water of precipitation, and adsorption temp is an outside temperature, 0～40 ℃ of its temperature range.Seawater after absorption can be used as refrigerated sea water and uses, and can be used as the raw material of evaporating brine, and also can directly arrange the sea.
(2) wash-out
In adsorbing saturated zeolite, feed tap water, the seawater in the zeolite is ejected; In zeolite, feed ammonium sulfite solution again, with ammonium sulfite solution with the K on the zeolite
+Wash, obtain rich potassium mother liquor, potassium type zeolite becomes ammonium type zeolite.At this moment, K in the rich potassium mother liquor
+Than about 30 times of enrichments in the seawater, make K
+Content is the rich potassium mother liquor of 12.01～13.03 grams per liters.
Ammonium solution+KZ → rich potassium mother liquor+NH
4Z
The ammonium sulfite solution that is used for wash-out is formulated at normal temperatures by ammonium sulphite and water, and ammonium sulfite solution concentration is ammonium sulphite content 100～150 grams per liters.The main chemical constitution of the rich potassium mother liquor of wash-out gained is: potassium sulfite (K
2SO
3) 24.32～26.39 grams per liters, ammonium sulphite { (NH
4)
2SO
382.14～130.64 grams per liters.
After adsorbing saturated zeolite wash-out and obtaining rich potassium mother liquor, potassium type zeolite becomes ammonium type zeolite, with sodium chloride solution ammonium type zeolite is converted into na-pretreated zeolite again, and obtains ammonium salt-containing water.Zeolite after the regeneration is reused for the potassium ion K in the adsorbing seawater in the absorption process
+
Sodium salt solution+NH
4Z → ammonium salt-containing water+NaZ
The sodium chloride solution of regeneration usefulness is that Industrial Salt adds the saturated brine that water is made, and regeneration temperature is an outside temperature, 0～40 ℃ of temperature range.Ammonium salt-containing water after the regeneration is used to reclaim ammonium or as the system alkali raw material of soda factory.
(3) ammonia still process
In the rich potassium mother liquor of wash-out gained, according to ammonium sulphite in the solution: the mol ratio of potassium hydroxide is that 1: 2 ratio is allocated potassium hydroxide into, stirring and dissolving.Ammonium sulphite { (NH in the rich potassium mother liquor
4)
2SO
3Generate potassium sulfite (K with potassium hydroxide (KOH)
2SO
3) and ammonia (NH
4OH).
Again with the above-mentioned rich potassium mother liquor of allocating potassium hydroxide at 80～90 ℃ of heating evaporations, with the form evaporable ammonia (NH of gas phase
3) through condensation absorb ammoniacal liquor, the liquid phase after the ammonia still process is referred to as ammonia still process and finishes liquid.Ammonia still process finishes that main component is potassium sulfite (K in the liquid
2SO
3) and water.
(4) evaporation concentration
The further evaporation concentration of liquid is finished in ammonia still process, potassium sulfite concentration is improved, be evaporated to 105 ℃.
(5) cooling
To finish liquid cooling but after the evaporation concentration, make the potassium sulfite concentrated solution.The type of cooling can be the tubulation cooling or adopts the negative pressure of vacuum cooling, and complete evaporation of liquid is cooled to below 40 ℃, so that liquid packaging.
The present invention be a kind of be the novel method of raw material production potassium sulfite with the seawater, produce the part potassium ion K of potassium sulfite
+Come from potassium from sea water, opened up new potassium resource.Simultaneously, the byproduct that another raw material ammonium sulphite of producing potassium sulfite is the present ammonia process of desulfurization, product price is relatively low.The ammoniacal liquor of producing by-product in the potassium sulfite process can be used as the fertile use of farming, also can be used as the raw material of producing other Chemicals simultaneously.Be used for absorption and wash-out potassium ion K
+Zeolite, can be by using repeatedly after the regeneration.Therefore, potassium sulfite preparation method involved in the present invention has the advantage that raw material sources are wide, production cost is low than the method for prior art.
Embodiment
Embodiment one
Get six glass exchange columns (15 * 1410 millimeters of φ), every post filling zeolite weight 200 grams, about 1150 millimeters of zeolite loading height.Above-mentioned six zeolite column series connection is used, got Tanggu, Tianjin New Port seawater, its seawater component is as follows: K
+0.371 grams per liter, Ca
2+0.390 grams per liter, Mg
2+1.220 grams per liter, Cl
-18.360 grams per liter.Above-mentioned seawater is fed the zeolite exchange post, and the flow rate control of seawater in the zeolite exchange post is in 70 ml/min, and feeding the seawater amount is 116 liters, K in the seawater of absorption back
+0.167 grams per liter, this moment, zeolite adsorbed saturatedly substantially, finished absorbing unit operation, and zeolite became potassium type zeolite by the sodium type after absorption was finished.
Utilize ammonium sulphite and water to prepare ammonium sulfite solution at normal temperatures, ammonium sulphite concentration is (NH
4)
2SO
3100 grams per liters.To carry out wash-out in 1200 milliliters the above-mentioned ammonium sulfite solutions feeding zeolite column, the flow rate control of ammonium sulfite solution in zeolite column is in 20 ml/min, and wash-out gets 1200 milliliters of rich potassium mother liquors, and rich potassium mother liquor consists of: K
2SO
324.32 grams per liter, (NH
4)
2SO
3) 82.14 grams per liters.After wash-out was finished, zeolite became ammonium type zeolite by potassium type zeolite.
Utilize Industrial Salt to add water preparation saturated nacl aqueous solution, sodium chloride concentration is NaCl 320 grams per liters.To regenerate in 3600 milliliters of saturated nacl aqueous solutions feeding zeolite column.The control saturated nacl aqueous solution feeds flow velocity in the zeolite column in 20 ml/min, and regeneration gained solution is referred to as regenerated liquid, regenerated liquid consist of NH
4 +8.65 grams per liter, K
+1.71 grams per liter, Na
+113.75 grams per liter.After regeneration was finished, zeolite became na-pretreated zeolite by the ammonium type, is used for the ion exchange process that " absorption-wash-out-regeneration " carried out in next circulation.
Get 1200 milliliters rich potassium mother liquor (its weight 1300 grams), its composition is K
2SO
324.32 grams per liter, (NH
4)
2SO
382.14 grams per liter.In rich potassium mother liquor, add potassium hydroxide 95.17 grams, stirring and dissolving.The rich potassium mother liquor that adds potassium hydroxide is steamed ammonium, be evaporated to 85 ℃, the gas phase cooling and absorbing of evaporating is got ammoniacal liquor 192.60 grams (ammonia concentration is 15%), and liquid 1202.57 grams are finished in acquisition ammonia still process.
Liquid heating evaporation in vaporizer is finished in above-mentioned ammonia still process, stopped heating when being evaporated to 105 ℃, evaporation moisture content 712.57 grams get one section complete evaporation of liquid, 490 grams, and feed liquid proportion is 1.35, and volume is 363 milliliters, its K
2SO
3Concentration is 450 grams per liters.With above-mentioned complete evaporation of liquid cooling, cooling temperature to 40 ℃, the potassium sulfite cooling solution.
Embodiment two
Get six glass exchange columns (15 * 1410 millimeters of φ), every post filling zeolite weight 200 grams, about 1150 millimeters of zeolite loading height.Above-mentioned six zeolite column series connection is used, got Tanggu, Tianjin New Port seawater, its seawater component is as follows: K
+0.371 grams per liter, Ca
2+0.390 grams per liter, Mg
2+1.220 grams per liter, Cl
-18.360 grams per liter.Above-mentioned seawater is fed the zeolite exchange post, and the flow rate control of seawater in the zeolite exchange post is in 70 ml/min, and feeding the seawater amount is 116 liters, K in the seawater of absorption back
+0.167 grams per liter, this moment, zeolite adsorbed saturatedly substantially, finished absorbing unit operation back zeolite and became potassium type zeolite by the sodium type.
Utilize ammonium sulphite and water to prepare ammonium sulfite solution at normal temperatures, ammonium sulphite concentration is (NH
4)
2SO
3150 grams per liters.To carry out wash-out in 1200 milliliters the above-mentioned ammonium sulfite solutions feeding zeolite column, the flow rate control of ammonium sulfite solution in zeolite column is in 20 ml/min, and wash-out gets 1200 milliliters of rich potassium mother liquors, and rich potassium mother liquor consists of K
2SO
324.32 grams per liter, (NH
4)
2SO
3) 132.14 grams per liters.After wash-out was finished, zeolite became ammonium type zeolite by potassium type zeolite.
Utilize Industrial Salt to add water preparation saturated nacl aqueous solution, sodium chloride concentration is NaCl 320 grams per liters.To regenerate in 3600 milliliters of saturated nacl aqueous solutions feeding zeolite column.The flow velocity of control saturated nacl aqueous solution in zeolite column is 20 ml/min.Regeneration gained solution is referred to as regenerated liquid, regenerated liquid consist of NH4+ 8.65 grams per liters, K+ 1.71 grams per liters, Na+113.75 grams per liter.After regeneration was finished, zeolite became na-pretreated zeolite by the ammonium type, is used for the ion exchange process that " absorption-wash-out-regeneration " carried out in next circulation.
Get 1200 milliliters rich potassium mother liquor (weight 1300 grams), its composition is K2SO3 24.32 grams per liters, (NH4) 2,SO3 132.14 grams per liters.In rich potassium mother liquor, add potassium hydroxide 153.10 grams, stirring and dissolving.The rich potassium mother liquor that adds potassium hydroxide is steamed ammonium, be evaporated to 95 ℃, the gas phase cooling and absorbing of evaporating is got ammoniacal liquor 331.98 grams (ammonia concentration is 14%), obtain ammonia still process and finish liquid 1121.12 grams.
Liquid heating evaporation in vaporizer is finished in above-mentioned ammonia still process, stopped heating when being evaporated to 110 ℃, evaporation moisture content 402.12 grams get one section complete evaporation of liquid, 719 grams, and feed liquid proportion is 1.35, and volume is 532 milliliters, and K2SO3 concentration is 460 grams per liters.With above-mentioned complete evaporation of liquid cooling, cooling temperature to 40 ℃, the potassium sulfite cooling solution.
Claims (7)
1. method of utilizing seawater to produce potassium sulfite is characterized in that processing step comprises: with the natural zeolite mineral ion sorbent material, and the potassium ion in the adsorbing seawater; Be eluent with the ammonium sulfite solution again, the potassium ion on the natural zeolite washed that obtain containing the rich potassium mother liquor of potassium, ammonium, sulfite ion, ammonium sulfite solution concentration is ammonium sulphite content 100～150 grams per liters; To add the rich potassium mother liquor heating ammonia still process of potassium hydroxide again, and make ammonia still process and finish liquid; The further evaporation concentration of liquid is finished in ammonia still process, and cooling makes the potassium sulfite concentrated solution then.
2. the method for utilizing seawater to produce potassium sulfite according to claim 1 is characterized in that, with the potassium ion in the natural zeolite adsorbing seawater, the adsorption temp scope is 0～40 ℃.
3. the method for utilizing seawater to produce potassium sulfite according to claim 1 is characterized in that, the ammonium sulfite solution that is used for eluent is formulated at normal temperatures by ammonium sulphite and water; To adsorb after seawater ejects in the saturated zeolite by the tap water that feeds, feed ammonium sulfite solution again, the potassium ion on the zeolite will be washed, obtain rich potassium mother liquor.
4. the method for utilizing seawater to produce potassium sulfite according to claim 1 is characterized in that, according to ammonium sulphite in the solution: the mol ratio of potassium hydroxide is that 1: 2 ratio is allocated potassium hydroxide into, stirring and dissolving in rich potassium mother liquor.
5. the method for utilizing seawater to produce potassium sulfite according to claim 1 is characterized in that, the rich potassium mother liquor of allocating potassium hydroxide at 80～90 ℃ of heating evaporations, is obtained ammonia still process and finishes liquid.
6. the method for utilizing seawater to produce potassium sulfite according to claim 1 is characterized in that, the further evaporation concentration of liquid is finished in ammonia still process, is evaporated to 105 ℃.
7. the method for utilizing seawater to produce potassium sulfite according to claim 1 is characterized in that, will finish liquid cooling but after the evaporation concentration, and complete evaporation of liquid is cooled to below 40 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910310617 CN101717099B (en) | 2009-11-30 | 2009-11-30 | Method for preparing potassium sulfite by using sea water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910310617 CN101717099B (en) | 2009-11-30 | 2009-11-30 | Method for preparing potassium sulfite by using sea water |
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|---|---|
| CN101717099A CN101717099A (en) | 2010-06-02 |
| CN101717099B true CN101717099B (en) | 2011-10-12 |
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|---|---|---|---|---|
| CN106430252A (en) * | 2016-11-30 | 2017-02-22 | 东至天孚化工有限公司 | Concentrating process for extracting potassium sulfite by seawater |
| CN111439759A (en) * | 2020-05-23 | 2020-07-24 | 淄博长城化工厂 | Method for producing food-grade potassium sulfite by adopting potassium metabisulfite mother liquor |
| CN111634927A (en) * | 2020-06-02 | 2020-09-08 | 山东仲雅信息技术有限公司 | Production method of food-grade potassium sulfite |
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Granted publication date: 20111012 Termination date: 20121130 |