CN104909389B - A kind of method preparing coproduction of potassium sulfate potassium hydroxide - Google Patents
A kind of method preparing coproduction of potassium sulfate potassium hydroxide Download PDFInfo
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- CN104909389B CN104909389B CN201510290986.5A CN201510290986A CN104909389B CN 104909389 B CN104909389 B CN 104909389B CN 201510290986 A CN201510290986 A CN 201510290986A CN 104909389 B CN104909389 B CN 104909389B
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- filtrate
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- methyl alcohol
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/20—Preparation by reacting oxides or hydroxides with alkali metal salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/06—Preparation of sulfates by double decomposition
- C01D5/08—Preparation of sulfates by double decomposition with each other or with ammonium sulfate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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Abstract
A kind of method preparing coproduction of potassium sulfate potassium hydroxide, by KHSO4With Ca (OH)2Reacting 1.5 hours at 90 DEG C 100 DEG C after dissolving respectively and sizing mixing, control reaction temperature, filter the most while hot and also filter with hot wash, filter residue adds sulfuric acid and adjusts pH to be to obtain CaSO after acidity4；Filtrate adds methyl alcohol stirring, filters and separate to obtain K2SO4Solid and mixing filtrate；Gained mixing filtrate distillation, respectively obtains methyl alcohol, water, residue raffinate, residue raffinate, by being concentrated by evaporation and cooling clarification, prepares containing 45%～50% potassium hydroxide solution.Present invention process is simple, and product quality is high, and raw material are cheap, it is simple to industrial applications, and can realize resource circulation utilization by containing methyl alcohol mixing filtrate distillation, and accessory substance potassium hydroxide also has higher economic worth simultaneously.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to one and utilize potassium acid sulfate and calcium hydroxide to prepare coproduction of potassium sulfate
The method of potassium hydroxide.
Background technology
Potassium sulfate, as a kind of important potash fertilizer of high-quality without chlorine, is widely used in agricultural production, and it not only can improve agricultural production
Quality, moreover it is possible to improving its quality, friend is liked by vast farmers.But sylvite is a kind of non-renewable resources,
And the distributed pole imbalance in the whole world, the most on the Northern Hemisphere, the most Canadian and former Soviet Union accounts for world's sylvite total resources respectively
The 40% and 37% of amount.Remaining known reserve is distributed in the ground such as the U.S., Europe, the Middle East, Thailand, the Congo.
China is lean potassium country, and potassium resource is mainly distributed on northwest, southwest, in the recent period, border, Songzi City, middle part Hubei Province
The most also verify reserves and reach the Potash Resources of 4,800,000,000 tons.China is one of sylvite country of consumption maximum in the world, needs every year
Consuming about more than 1,100 ten thousand tons of sylvite, sylvite is inorganic and organic products kind has reached more than 100 and planted, and the sylvite annual production of China
Being only about 3,500,000 tons, 70% dependence on import, sylvite has become one of anxious grand strategy goods and materials lacked of China.
But the demand of sylvite is incremented by by China every year constantly, huge demand gap, provide extensively for sylvite market
Wealthy prospect.At present, supply falls short of demand for whole world sylvite, and price rises steadily.But the life of sylvite especially high-quality potassium sulfate
Product technology is maintained secrecy by Some Enterprises always, and the potassium sulfate how producing high-quality annoyings Chemical Manufacture enterprise always.
Summary of the invention
It is an object of the invention to for problem above, it is provided that one utilizes potassium acid sulfate and calcium hydroxide to prepare coproduction of potassium sulfate
The method of potassium hydroxide, it is achieved recycling and maximization of economic benefit of resource.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is: one prepares coproduction of potassium sulfate potassium hydroxide
Method, its chemical equation is:
2KHSO4+Ca(OH)2=CaSO4↓+K2SO4+2H2O
K2SO4+Ca(OH)2=CaSO4↓+KOH
Concretely comprise the following steps:
1) by KHSO4With Ca (OH)21:1.2～1.5 weighs in molar ratio, adds water the most respectively and dissolves and size mixing
Obtain KHSO4Solution and Ca (OH)2Emulsion, then by the KHSO of gained4Solution and Ca (OH)2Emulsion mixes,
React 1～1.5 hour at 90-100 DEG C；
2) step 1) material of gained filters at 88-95 DEG C maintaining, and the filter residue of gained is washed with more than 90 DEG C water
Filter, then in filter residue, add H2SO4, regulation PH obtains CaSO to neutrality4；
3) step 2) in the filtrate that obtains after high temperature filtration adds methyl alcohol, obtain K after agitation and filtration2SO4Solid and filter
Liquid；The distillation of gained filtrate respectively obtains methyl alcohol, water and residue raffinate, by residue raffinate by being concentrated by evaporation and cooling down clear
Clearly, potassium hydroxide solution is obtained.
Little in view of the solubility of potassium sulfate own, and be influenced by temperature, high temperature filtration and guarantee wash water temperature are as far as possible
Improve the rate of recovery of potassium sulfate.Therefore the material of gained is about 90 DEG C filtrations, the filter residue of gained is washed with more than 90 DEG C water
Filter.
Step 3) utilize potassium sulfate and the potassium hydroxide dissolving situation in methyl alcohol to be efficiently separated out, therefore after filtration
To filtrate in add methyl alcohol.
Further, higher liquid-solid ratio is conducive to improving the amount of KOH in product, but too high liquid-solid ratio stirring is limited
System, comprehensive analytical procedure 1) in amount of water be KHSO4、Ca(OH)21.5 times of gross mass most suitable.
Step 2) in washing after filter filtrate collect, for step 1) in size mixing.
Step 2) in the CaSO that obtains4It is purified through repeatedly washing.
Step 3) in methyl alcohol add volume equal with the amount of filtrate.
Described step 3) in the methyl alcohol recycling that obtains of distillation, the water that obtains of distillation is in step 1) weight when dissolving and size mixing
Multiple utilization.
Described step 3) in the mass concentration of potassium hydroxide solution that steams be 45%～50%.
Present invention process is simple, and product quality is high, K2O content >=50%, it is simple to industrial applications, and with Ca (OH)2、
CaO is cheap as cost of material, low cost, good in economic efficiency；Methyl alcohol mixing filtrate distillation will be contained and can realize resources circulation
Utilizing, accessory substance potassium hydroxide also has higher economic worth simultaneously.
The advantage of this invention is that coproduction potassium hydroxide, a small amount of potassium hydroxide then substantially increase added value of product, but wants
Obtain potassium hydroxide, be necessary for the calcium hydroxide of a large amount of excess and relatively low liquid-solid ratio in the reaction.The most unreacted
Calcium hydroxide remains in calcium sulfate filter cake, one be waste, two be bad again with, in the present invention use gradient cross
Effective this difficult problem solved of reaction.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment and accompanying drawing, but the scope of protection of present invention is not limited to reality
Execute the scope of example statement.Its technological process is as shown in Figure 1.
Embodiment 1:
A kind of method preparing coproduction of potassium sulfate potassium hydroxide, concretely comprises the following steps:
1)KHSO4With Ca (OH)21:1 weighs in molar ratio, weighs KHSO respectively4272g and Ca (OH)2148g,
Add 500ml water to KHSO4Carry out heating for dissolving, add 150ml water to Ca (OH)2Size mixing；Then molten by gained
Liquid mixes, and reacts 1h at 90-100 DEG C；
2) step 1) material of gained directly filters, and filtration temperature maintains about 90 DEG C, obtains the filter of about 550ml
Liquid, the filter cake of gained 500ml, twice washing and filtering of more than 90 DEG C moisture altogether, filtrate that washing obtains and before
550ml filtrate is admixed together amounts to about 1040ml.Dilute H is added again in filter residue2SO4And stir, regulation PH is to neutral
Obtain CaSO4；
3) step 2) filter after the filtrate 1:1 by volume that obtains add methyl alcohol 1040ml and stir, potassium sulfate now base
This all separates out, and obtains K after filtration2SO4Solid 151g and filtrate, filtrate is the aqueous solution of methyl alcohol, potassium hydroxide；Institute
Obtain filtrate distillation and respectively obtain methyl alcohol, water and residue raffinate, residue raffinate is passed through evaporation and concentration and cooling clarification, obtains liquid
Body potassium hydroxide concentrate 20g, its mass concentration is 15%.
Gained K2SO4Analyze K2O%=50.2%.
Embodiment 2:
A kind of method preparing coproduction of potassium sulfate potassium hydroxide, concretely comprises the following steps:
1)KHSO4With Ca (OH)2Weigh than 1:1.2 by mol, weigh KHSO respectively4272g and
Ca(OH)2178g, adds 500ml water to KHSO4Carry out heating for dissolving, add 180ml water to Ca (OH)2Size mixing；
Then the solution of gained is mixed, react 1h at 90-100 DEG C；
2) step 1) material of gained directly filters, and filtration temperature maintains about 90 DEG C, obtains the filter of about 570ml
Liquid, the filter cake of gained 500ml, twice washing and filtering of more than 90 DEG C moisture altogether, filtrate that washing obtains and before
570ml filtrate is admixed together amounts to about 1050ml.Dilute H is added again in filter residue2SO4And stir, regulation PH is to neutral
Obtain CaSO4；
3) step 2) filter after the filtrate 1:1 by volume that obtains add methyl alcohol 1050ml and stir, potassium sulfate now base
This all separates out, and obtains K after filtration2SO4Solid 140g and filtrate, filtrate is the aqueous solution of methyl alcohol, potassium hydroxide；Institute
Obtain filtrate distillation and respectively obtain methyl alcohol, water and residue raffinate, residue raffinate is passed through evaporation and concentration and cooling clarification, obtains liquid
Body potassium hydroxide concentrate 20g, its mass concentration is 46%.
Gained K2SO4Analyze K2O%=51.0%.
Embodiment 3:
As it is shown in figure 1, a kind of method preparing coproduction of potassium sulfate potassium hydroxide, concretely comprise the following steps:
1)KHSO4With Ca (OH)2Weigh than 1:1.5 by mol, weigh KHSO respectively4272g and
Ca(OH)2222g, adds 500ml water to KHSO4Carry out heating for dissolving, add 220ml water to Ca (OH)2Size mixing；
Then the solution of gained is mixed, react 1h at 90-100 DEG C；
2) step 1) material of gained directly filters, and filtration temperature maintains about 90 DEG C, obtains the filter of about 600ml
Liquid, the filter cake of gained 500ml, twice washing and filtering of more than 90 DEG C moisture altogether, filtrate that washing obtains and before
600ml filtrate is admixed together amounts to about 1070ml.Dilute H is added again in filter residue2SO4And stir, regulation PH is to neutral
Obtain CaSO4；
3) step 2) filter after the filtrate 1:1 by volume that obtains add methyl alcohol 1070ml and stir, potassium sulfate now base
This all separates out, and obtains K after filtration2SO4Solid 132g and filtrate, filtrate is the aqueous solution of methyl alcohol, potassium hydroxide；Institute
Obtain filtrate distillation and respectively obtain methyl alcohol, water and residue raffinate, residue raffinate is passed through evaporation and concentration and cooling clarification, obtains liquid
Body potassium hydroxide concentrate 30g, its mass concentration is 47%.
Gained K2SO4Analyze K2O%=50.7%.
Claims (5)
1. the method preparing coproduction of potassium sulfate potassium hydroxide, it is characterised in that concretely comprise the following steps:
1) by KHSO4With Ca (OH)21:1.2 ~ 1.5 weigh in molar ratio, and adding water the most respectively, carrying out dissolves and size mixing obtains KHSO4Solution and Ca (OH)2Emulsion, then by the KHSO of gained4Solution and Ca (OH)2Emulsion mixes, and reacts 1 ~ 1.5 hour at 90-100 DEG C；
2) material of step 1) gained filters at 88-95 DEG C maintaining, and the filter residue of gained is with more than 90 DEG C water washing and filterings, then addition H in filter residue2SO4, regulation PH obtains CaSO to neutrality4；
3) step 2) in the filtrate that obtains after high temperature filtration adds methyl alcohol, obtain K after agitation and filtration2SO4Solid and filtrate；The distillation of gained filtrate respectively obtains methyl alcohol, water and residue raffinate, passes through to be concentrated by evaporation and cooling clarification by residue raffinate, obtains the potassium hydroxide solution that mass concentration is 45%～50%；Wherein distilling the methyl alcohol recycling obtained, the water that distillation obtains is recycling when step 1) is dissolved and sizes mixing.
Method the most according to claim 1, it is characterised in that: in step 1), amount of water is KHSO4、Ca(OH)21-2 times of gross mass.
Method the most according to claim 1, it is characterised in that: step 2) in washing after filter filtrate collect, sizing mixing in step 1).
Method the most according to claim 1, it is characterised in that: step 2) in the CaSO that obtains4It is purified through repeatedly washing.
Method the most according to claim 1, it is characterised in that: in step 3), the addition volume of methyl alcohol is equal with the amount of filtrate.
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| CN104909389B true CN104909389B (en) | 2016-09-07 |
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| CN107417307B (en) * | 2017-09-12 | 2020-11-06 | 化工部长沙设计研究院 | Preparation process of potassium sulfate for water-soluble drip irrigation |
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| CN1016774B (en) * | 1984-02-28 | 1992-05-27 | 窒素股份有限公司 | Dry process for neutralizing potassium sulfate produced from potassium chloride and sulfuric acid |
| US6692716B1 (en) * | 1998-10-13 | 2004-02-17 | Airborne Industrial Minerals, Inc. | Method of formulating alkali earth salts |
| CN101428832B (en) * | 2008-11-27 | 2010-12-22 | 莱芜钢铁股份有限公司 | Potassium sulfate extracted from sintering dust separation ash and method for producing the same |
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