CN1037428C - Method for producing potassium sulfate by double decomposition of sodium sulfate and potassium chloride - Google Patents
Method for producing potassium sulfate by double decomposition of sodium sulfate and potassium chloride Download PDFInfo
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- CN1037428C CN1037428C CN95111303A CN95111303A CN1037428C CN 1037428 C CN1037428 C CN 1037428C CN 95111303 A CN95111303 A CN 95111303A CN 95111303 A CN95111303 A CN 95111303A CN 1037428 C CN1037428 C CN 1037428C
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- Prior art keywords
- reaction
- repone
- water
- mother liquor
- glaserite
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 title claims abstract description 30
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 17
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 10
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000001103 potassium chloride Substances 0.000 title abstract description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 title abstract description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 title abstract description 3
- 235000011151 potassium sulphates Nutrition 0.000 title abstract description 3
- 238000000354 decomposition reaction Methods 0.000 title abstract 4
- 235000011164 potassium chloride Nutrition 0.000 title abstract 2
- 239000012452 mother liquor Substances 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 208000006558 Dental Calculus Diseases 0.000 claims description 14
- 238000005649 metathesis reaction Methods 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 5
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000007832 Na2SO4 Substances 0.000 abstract 1
- 239000012736 aqueous medium Substances 0.000 abstract 1
- 239000010446 mirabilite Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 239000000543 intermediate Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention relates to a technological process for producing potassium sulfate by using sodium sulfate and potassium chloride as raw material and adopting two-step double decomposition reaction in aqueous medium, and is characterized by that the glaserite (3K) produced by first-step double decomposition reaction2SO4，Na2SO4) Mother liquor is directly cooled to separate mirabilite (Na)2SO4，10H2O) is recycled as a raw material; the second double decomposition reaction is carried out at 40-130 ℃, and the mixture is stirred for 30 minutes to obtain K2More than or equal to 50 percent of O and less than or equal to 1.5 percent of C, and the total recovery rate (by K)2Calculated by O) is more than or equal to 98 percent.
Description
The present invention relates to the manufacture method of a kind of sodium, potassium or general alkali-metal vitriol.
Vitriolate of tartar mainly decomposes method, promptly so-called Mannheim method and the manufacturing of improving one's methods thereof of Repone K at present as main chlorideless potassic fertilizer product with sulfuric acid.Owing to need handle deep-etching material (H down at high temperature (700 ℃ of reaction zones and burner hearth up to more than 1200 ℃)
2SO
4, HCl), therefore, the apparatus cost height, working condition is abominable.
Recently, people begin to watch attentively with the manufacturing of the metathesis process in water medium vitriolate of tartar.Wherein the most noticeable be the German Messo 1985-1992 of company succeed in developing, by sodium sulfate and Repone K under normal temperature (25 ℃), through glaserite [3K
2SO
4.Na
2SO
4Or NaK
3(SO
4)
2] two step process of intermediate are [referring to documents Phosphorus ﹠amp; Potassium No.178, Mar-Apr 1992, P20-26].The reaction formula of two-step reaction is respectively:
The shortcoming of Messo method and other technology of metathesis production vitriolate of tartar in water by sodium sulfate and Repone K is, above-mentioned two step replacement(metathesis)reactions relate to solid phase with the material exchange alternate with solid-liquid, the nucleus of Chan Shenging and very easily produce absorption, the occlusion of impurity and carry secretly at normal temperatures at growth process, make product impure, thereby:
1, the reactor that needs particular design, promptly so-called pipe core shaft type crystallizer is controlled degree of supersaturation, thereby has improved apparatus cost.
2, the first step reaction needed for two steps finished again.This is because in order to reach K
2The maximum yield of O, mother liquor are formed and should be formed near the common saturation point of sodium sulfate, sodium-chlor and glaserite as far as possible, but the glaserite intermediate K that generates this moment
2O: Na
2O (mol) has only (2.2-2.4): 1 (theoretical value is 3: 1) must further make K with the Repone K reaction
2O: Na
2O (mol) reaches more than 2.7: 1, just can be used for the reaction of second step, otherwise the product vitriolate of tartar is off quality, and this is one of committed step of Messo method.
Even 3 have adopted the reactor of particular design, the vitriolate of tartar crude product that the reaction of second step produces must just can be produced qualified potassium product through one washing procedure, i.e. second step reaction also needed for two steps finished, and the art breading water yield is increased, and energy consumption increases.
4, product vitriolate of tartar purity is low, has only 87.5-92.1% (to contain K
2O47.3-49.8%), do not reach current in the world agricultural grade vitriolate of tartar quality standard (K as yet
2O 〉=50%, Cl≤1.5%), after the washing purification process, also just can reach 96.0-98.0% and (contain K
2O
51.9-53.0%).China's Qinghai potash fertilizer plant can only be produced K
2O 〉=45% product.
The objective of the invention is: do not have " three wastes " discharging and total recovery (K in technological process
2The O meter) 〉=98% under the prerequisite, provide a kind of product purity height (K
2O 〉=50%, Cl≤1.5%), technical process is simple, and is with short production cycle, do not need specific equipment, and economic benefit and environmental benefit be the production method of the good vitriolate of tartar that is easy to apply all.
Accompanying drawing 1 is a technological process block-diagram of the present invention.
1 pair of implementation step of the present invention is described as follows by reference to the accompanying drawings:
(1) the first step replacement(metathesis)reaction
With round-robin and additional Repone K, round-robin and the sodium sulfate or the saltcake (Na that replenish
2SO
4.10H
2O), round-robin and the water that replenishes and round-robin Repone K mother liquor and potassium sulfate mother liquid are pressed KCl: Na
2SO
4: H
2O=1: (1.5-2.0): (2.5-3.0) weight ratio was 23-26 ℃ of following stirring reaction 6 hours.Filter (centrifugal) and go out glaserite, the gained liquid phase is that the glaserite mother liquor is cooled to 0 ℃, separates out saltcake Na
2SO
4.10H
2O, its filtration (centrifugal) is separated, gained solid saltcake returns the utilization of the first step reaction cycle, the gained liquid phase is that the saltcake mother liquor must be paid product sodium-chlor by solid through evaporation, thickening filtration (centrifugal), the water of evaporation reclaims through condensation and makes the first step and second step reaction batching water, and elimination sodium-chlor is mother liquid obtained, is cooled to room temperature, filter (centrifugal) and obtain the raw material recycle that solid Repone K is done the first step or second step, the mother liquor of elimination Repone K returns the utilization of the first step reaction cycle.
(2) second step replacement(metathesis)reactions
With the solid glaserite that the first step Reaction Separation goes out,, press KCl: glaserite: H with fresh and circulation Repone K and fresh and recirculated water
2O (weight ratio) 1: (1.4-1.6): (2.0-2.4) proportioning is filtered (centrifugal) and is obtained K 40-130 ℃ of following stirring reaction 30 minutes
2O 〉=50%, the potassium product of Cl≤1.5%, its mother liquor return the utilization of the first step reaction cycle.
The first step replacement(metathesis)reaction also can be carried out under comparatively high temps (40-100 ℃), thereby will shorten to half an hour approximately the reaction times.But reaction mass must be cooled to 25 ℃ of separation, the glaserite yield is improved, the more important thing is, sodium chloride concentration maximum in the glaserite mother liquor that only under 25 ℃, obtains (about 23.4%), thereby evaporated water minimum when making the back reclaim NaCl.Therefore it is not obvious that the first step is reacted the benefit of at high temperature carrying out.
From thermodynamics (phasor) angle, the second step replacement(metathesis)reaction is at high temperature carried out K
2The O yield can reduce, and therefore this reaction is for a long time all carried out at 25 ℃.But careful calphad shows, vitriolate of tartar itself and Repone K and glaserite altogether 25 ℃ of solubleness in the saturated solution be 2.1%, 50 ℃ to be 1.9%, 60 ℃ be 2.0%, 100 ℃ of ability 2.7%, therefore since the rising of temperature to K
2The reduction of O yield influence is very little, and this is because KCl concentration increases the common-ion effcet that is produced have been compensated temperature and raise to the influence of yield, solubility change this two kinds of results that factor disappears and rises just under the differing temps; On the other hand, owing to vitriolate of tartar crude product of the present invention does not need further to wash purifying, thereby actual recovery also can improve.
The present invention compares with the Messo method owing to the crystallization purity height that produces under comparatively high temps, and the crude product vitriolate of tartar need just can not reach K through the washing purification step
2O 〉=50%, the quality standard of Cl≤1.5% (actual≤1.0%) if further wash purifying, can make product K
2SO
4Purity reaches more than 99%, thereby satisfies technical grade, pharmaceutical grade or other product requirement to purity requirement.
The present invention is keeping the Messo method not have discharging and total K
2On the basis of O rate of recovery height (〉=98%), reduced by four procedures, eliminated the requirement of the reactor of particular design.Simultaneously, since same when pyroreaction can shorten reaction greatly, labour productivity and plant factor improved; Owing to need not wash the purifying water, the art breading water yield is reduced again.Therefore the present invention descends apparatus cost and production cost significantly; Also, two-step reaction lays the foundation continuously for being incorporated in the reactor.
Relatively seeing the following form of the present invention and Messo method:
| Reactor | The second step temperature of reaction | Processing step | Thick product purity | Purified product purity | |
| Messo technology | Particular design | ～25℃ | 14 | 87.5- 92.1％ | 96.0- 98.0％ |
| Technology of the present invention | Universal | 40-130℃ | 10 | 92.5- 94.5％ | 99.0％ |
If being reflected under the comparatively high temps (for example 〉=40 ℃), carry out in the first step and second step, some other factor then, as the addition sequence of reactant with add implantation site, alr mode and speed, type of heating and heat-up rate etc., the influence of technology and product purity is seemed inessential.Reactant (KCl, Na
2SO
4, glaserite and water) can add simultaneously or any material adds earlier and adds other material gained result again and do not have significant difference.Stirring velocity can be selected in 80-300 rev/min.
Temperature of reaction of the present invention generally just can obtain satisfied result down at 50-90 ℃.At higher temperature, reaction gained result and 50-90 ℃ of reaction gained result do not have significant difference under the boiling point (110-130 ℃) of solution.Reaction of the present invention is all carried out under normal pressure, is being nonsensical above reaction under the boiling point, only can increase energy consumption and make process complicated.
Below three embodiment the invention will be further described.
Embodiment 1:
With 142 gram Na
2SO
4(99%) and 90 gram KCl (Jordan produces, K
2O 〉=60%) and 240 gram water stirred 6 hours down at room temperature 23-26 ℃, suction filtration, oven dry, glaserite intermediate 120 grams.This intermediate is divided into two parts, and portion is done following experiment, and portion compares experiment.
Get 60 gram glaserite intermediates, (Jordan produces, K to add 40.6 gram KCl
2O 〉=60%), water 94 gram stirs down and is heated to 45-55 ℃, under this temperature, reacted 30 minutes, suction filtration, dry product K
2SO
454.8 gram, it is as follows to press ZBG 21006-89 national standard analytical results:
K
2O 50% Cl is water 0.6% O.6%
Control experiment:
40 gram embodiment 1 gained glaserite intermediates add 27.1 gram KCl, 64 gram water, be interrupted stir under, room temperature reaction one day, suction filtration, dry product vitriolate of tartar 40.6 grams, analytical results:
K
2O 46.6% Cl 4.12% water 0.6%
Embodiment 2:
With thick potassium product 30 grams of gained in the reference examples, (Jordan produces, K to add water 24 gram KCl
2O 〉=60%) 6.5 grams, 70-80 ℃ of stirring reaction 30 minutes, suction filtration, dry K
2SO
4Product 26.7 grams, analytical results:
K
2O 53.5% Cl O.3% water 0.2% (is equivalent to 99%K
2SO
4)
Embodiment 3:
Take by weighing 180 gram Na
2SO
4(99%), (Jordan produces 100 gram KCl, K
2O 〉=60%), 280 gram water stirred 6 hours down in room temperature (24-26 ℃), suction filtration, dry glaserite intermediate 128 grams, get 100 gram glaserites wherein, (Jordan produces, K to add 64.5 gram KCl
2O 〉=60%), 140 gram water, (about 125 ℃ of temperature of reaction) stirring reaction is 30 minutes under refluxing, and cold slightly back suction filtration is dried to such an extent that potassium product 89 restrains analytical results:
K
2O 51.1% Cl 0.1% water 0.2%
Claims (1)
1, a kind of method of making vitriolate of tartar by sodium sulfate and Repone K metathesis is characterized in that the first step reaction is by Repone K: sodium sulfate: water is 1: (1.5-2.0): weight ratio (2.5-3.0), 23-26 ℃ of reaction 6 hours, leach glaserite, mother liquid obtainedly be cooled to 0 ℃, separate out saltcake (Na
2SO
4.10H
2O) return the utilization of the first step reaction cycle, the mother liquor of elimination saltcake obtains paying a product sodium-chlor through evaporating, concentrate, filtering, the water condensation of evaporation reclaims makes the first step and second step reaction batching water, the mother liquor of elimination sodium-chlor, be cooled to the room temperature filtration and obtain the raw material recycle that Repone K is done the first step and second reaction, the mother liquor of elimination Repone K returns the utilization of the first step reaction cycle; The second step reaction is by Repone K: glaserite: water is 1: (1.4-1.6): weight ratio (2.0-2.4), 40-130 ℃ of following stirring reaction 30 minutes, filtration obtained K
2O 〉=50%, the potassium product of Cl≤1.5%, its mother liquor return the utilization of the first step reaction cycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111303A CN1037428C (en) | 1995-03-30 | 1995-03-30 | Method for producing potassium sulfate by double decomposition of sodium sulfate and potassium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111303A CN1037428C (en) | 1995-03-30 | 1995-03-30 | Method for producing potassium sulfate by double decomposition of sodium sulfate and potassium chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1132180A CN1132180A (en) | 1996-10-02 |
| CN1037428C true CN1037428C (en) | 1998-02-18 |
Family
ID=5078606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111303A Expired - Fee Related CN1037428C (en) | 1995-03-30 | 1995-03-30 | Method for producing potassium sulfate by double decomposition of sodium sulfate and potassium chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1037428C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390847A (en) * | 2011-07-27 | 2012-03-28 | 陈海通 | Production method for preparing potassium sulfate by potassium chloride-sodium sulfate method |
| CN103435074A (en) * | 2013-08-29 | 2013-12-11 | 四川国理锂材料有限公司 | Method for producing potassium sulfate from byproducts in lithium salt production process |
| CN103466662B (en) * | 2013-09-23 | 2015-04-01 | 河北工业大学 | Method for preparing potassium sulfate with large grain diameter by utilizing reaction crystallization |
| CN104925835B (en) * | 2015-07-01 | 2016-08-24 | 化工部长沙设计研究院 | A kind of technique of mirabilite method preparing potassium sulfate |
| CN107673374A (en) * | 2017-10-27 | 2018-02-09 | 中国轻工业长沙工程有限公司 | Steel mill sinters flue dust and desulfurization waste liquor method of comprehensive utilization |
| 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 |
|---|---|---|---|---|
| SU806606A1 (en) * | 1979-03-28 | 1981-02-23 | Всесоюзный Научно-Исследовательскийи Проектный Институт Галургии | Method of potassium sulfate production |
| 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 |
-
1995
- 1995-03-30 CN CN95111303A patent/CN1037428C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU806606A1 (en) * | 1979-03-28 | 1981-02-23 | Всесоюзный Научно-Исследовательскийи Проектный Институт Галургии | Method of potassium sulfate production |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN1132180A (en) | 1996-10-02 |
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