CN1034906A - A kind of method of producing vitriolate of tartar - Google Patents

A kind of method of producing vitriolate of tartar Download PDF

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Publication number
CN1034906A
CN1034906A CN 88105025 CN88105025A CN1034906A CN 1034906 A CN1034906 A CN 1034906A CN 88105025 CN88105025 CN 88105025 CN 88105025 A CN88105025 A CN 88105025A CN 1034906 A CN1034906 A CN 1034906A
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Prior art keywords
tartar
tertiary amine
vitriolate
alkyl tertiary
alkyl
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CN 88105025
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CN1013100B (en
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王志仁
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SHENYANG INST OF CHEMICAL INDUSTRY COMPREHENSIVE UTILIZATION
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SHENYANG INST OF CHEMICAL INDUSTRY COMPREHENSIVE UTILIZATION
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Priority to CN 88105025 priority Critical patent/CN1013100B/en
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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
    • C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A kind of method of producing vitriolate of tartar, it is to be raw material with industrial sulphuric acid or sulfur waste acid, Repone K, ammonia, under the effect of association agent alkyl tertiary amine, produce vitriolate of tartar, byproduct is an ammonium chloride, and it and traditional method compare, and it is simple to have technology, the reaction conditions gentleness, can utilize " three wastes ", the raw material comprehensive utilization does not have hydrogenchloride to produce, do not have characteristics such as hydrochloric acid recycling, corrosion and environmental pollution and product recovery rate height, cost is low, quality good, is fit to the industrial production of various scales.

Description

A kind of method of producing vitriolate of tartar
The present invention relates to a kind of productive method of chemical engineering of producing vitriolate of tartar.
At present, both at home and abroad hot method and PRODUCING POTASSIUM SULFATE BY DOUBLE DECOMPOSITION of adopting more.Hot method has mannheim (Mannheim) oven process, and it is that sulfuric acid and Repone K are generated sal enixum earlier under lower temperature, and pyroreaction generates vitriolate of tartar in the mannheim then.Also have Hargreaves (Hargreares) method, it is Repone K is levigate, group's ball, drying, feeds hot sulfurous gas, air, water vapor then and react in conversion chamber, to generate vitriolate of tartar.Above-mentioned these two kinds of method processing requirements are relatively harsher, all exist hydrogenchloride and recycle and hcl corrosion problems such as pollution.The subdivision method is to be raw material with Repone K, ammonium sulfate, and its mother liquor is handled numerous and diverse, and the rate of recovery of potassium is lower.
The purpose of this invention is to provide a kind of under the participation effect of alkyl tertiary amine, with the acid of industrial sulphuric acid or sulfur waste and Repone K directly conversion produce the production technique of vitriolate of tartar.
The object of the present invention is achieved like this: utilize sulfur waste acid, Repone K, ammonia after industrial sulphuric acid or industry are used to be raw material, under the effect of alkyl tertiary amine, can produce vitriolate of tartar and ammonium chloride through associating, replace, regenerating; Also can be through preparing, forming and put, regenerate and produce vitriolate of tartar and ammonium chloride.
Accompanying drawing 1 is the technical process with the present invention's association-substitution method.
Accompanying drawing 2 is that the present invention prepares-technical process of association method.
Below in conjunction with accompanying drawing technological process of the present invention is described in detail.
Accompanying drawing 1 association-displacement method technique
1, associates
The association agent is the hydrocarbon polymer that contains nitrogen, and general formula is R 3N is an alkyl tertiary amine.It has three alkyl, and each alkyl all is the alkyl with free functional group form, and the carbonatoms of alkyl is more than five or five.It is insoluble in water, can with sulfuric acid generation association reaction.
After industrial sulphuric acid or industry used later sulfur waste acid dilution, pump in the retort, add alkyl tertiary amine with the amount of 1: 0.9～2.6 mol ratio according to sulfuric acid and alkyl tertiary amine, under 5～150 ℃ of temperature, stirring reaction 0.1～8 hour.This moment, reaction process was:
R 3The N(organic phase)+H 2SO 4(water)=(R 3NH) HSO 4(organic phase)
Or 2R 3The N(organic phase)+H 2SO 4(water)=(R 3NH) 2SO 4(organic phase)
Leave standstill two then and be separated, the lower floor that tells is a water, is and forms Yu Shui, can be used as the dilution vitriol oil or drain.The upper strata is an organic phase, i.e. alkyl tertiary amine vitriol is stayed in the reaction narrow-necked earthen jar waiting and replaced.
2, displacement
Displacer is a Repone K.Will be through Klorvess Liquid that removes by filter impurity or the Klorvess Liquid that is dissolved with vitriolate of tartar, sal enixum, amount according to 1: 1.0～3.0 mol ratios of sulfuric acid in the alkyl tertiary amine hydrochlorate and Repone K, join in the reaction narrow-necked earthen jar, under 10～120 ℃ of temperature, stirring reaction 0.1～8 hour, this moment, reaction was:
Leave standstill two then and be separated, isolated lower floor is a water, is vitriolate of tartar or potassium hydrogen sulfate solution, is cooled to 10 ℃, treat the vitriolate of tartar crystallization separate out finish after, separate vitriolate of tartar, mother liquor is used as preparation Repone K.The upper strata is that organic phase is the alkyl tertiary amine hydrochloride, stays in the reaction narrow-necked earthen jar and regenerates waiting.
3, regeneration
Regenerator is the aqueous solution or the ammonium chloride solution that contains ammonia.According to the amount with 1: 0.8～1.4 mol ratios of hydrogenchloride in the alkyl tertiary amine hydrochloride and ammonia, ammoniacal liquor or ammoniated ammonium chloride solution are joined in the reaction narrow-necked earthen jar, under 10～150 ℃ of temperature, stirred 0.1～8 hour, carry out regenerative response.That is:
(R 3NH) CL(organic phase)+NH 3=R 3The N(organic phase)+NH 4The CL(water)
Leave standstill two then and be separated, isolated lower floor is a water, is ammonium chloride solution, arrive content 36～65% through evaporation concentration, under agitation be cooled to 10～20 ℃, obtain byproduct ammonium chloride after making the crystallization of ammonium chloride separate out separation, mother liquor can recycle as regenerator behind ammonia.
Accompanying drawing 2 is prepared-is formed and puts method technology
1, preparation
The mother liquor, water, Repone K that will contain vitriolate of tartar, sal enixum stirred 0.1～8 hour under 5～120 ℃ of temperature, made its dissolving and removed by filter impurity.Then according to sulfuric acid and Repone K with 1: 0.9～3.0 mol ratio.Drop into the sulfur waste acid after industrial sulphuric acid or industry are used, make its fully miscible preparation liquid that is stand-by.
2, form and put
The association agent is the hydrocarbon polymer that contains nitrogen, and general formula is R 3N is an alkyl tertiary amine.It has three each alkyl of alkyl all is the alkyl with free functional group form, and the carbonatoms of alkyl is more than five or five.It is insoluble in water, can with sulfuric acid generation association reaction.
Press sulfuric acid in the obtain solution and alkyl tertiary amine with 1: 0.9～2.6 mol ratio.Alkyl tertiary amine and preparation liquid pump are gone into to react in the narrow-necked earthen jar, under 5～150 ℃ of temperature, stirred 0.1～8 hour, form and put reaction.This moment, reaction formula was:
R 3The N(organic phase)+H 2SO 4(water)+KCL(water)=(R 3NH) CL(organic phase)+KHSO 4(water)
Or 2R 3The N(organic phase)+H 2SO 4(water)+2KCL(water)=2 (R 3NH) CL(organic phase)+K 2SO 4(water)
Leave standstill two then and be separated, the upper strata is an organic phase, and promptly the alkyl tertiary amine hydrochloride is stayed in the reaction narrow-necked earthen jar to treat the regeneration use.Lower floor is a water, i.e. vitriolate of tartar, potassium hydrogen sulfate solution are told postcooling to 10 ℃, the vitriolate of tartar crystallization separate out and finished product.As the dilute sulphuric acid that uses when associating, because concentration is low, need evaporation concentration make vitriolate of tartar concentration 20～30%, to put and separate out after being as cold as 10 ℃ of vitriolate of tartar crystallizations, mother liquor feeds intake as forming to put again.
3, regeneration
Regenerator is the aqueous solution or the ammonium chloride solution that contains ammonia.According to the hydrogenchloride in the alkyl tertiary amine hydrochloride and ammonia amount with 1: 0.8～1.4 mol ratios, ammoniacal liquor or ammoniated ammonium chloride solution joined in the reaction narrow-necked earthen jar go, under 10～150 ℃ of temperature, stirred 0.1～8 hour, carry out regenerative response.That is:
(R 3NH) CL(organic phase)+NH 3=R 3The N(organic phase)+NH 4The CL(water)
Leave standstill two then and be separated, lower floor is a water, is ammonium chloride solution, isolate after evaporation concentration to content 36～65%, under agitation is put into 10～20 ℃, ammonium chloride crystals is separated out, obtain byproduct ammonium chloride after the separation, mother liquor recycles as regenerator behind ammonia.
The present invention is owing to adopt the association method, and technology is simple, reaction conditions is gentle, production safety, can utilize " three wastes ", and the raw material comprehensive utilization does not have hydrogenchloride to produce, and does not exist hydrochloric acid to recycle, corrosion and pollution problem.The rate of recovery height of potassium, low, the good product quality of production cost, the industrial production of suitable various scales.
To be described further specific embodiments of the present invention by embodiment below:
Embodiment 1
517 kilograms of useless dilute sulphuric acids with 18% (rolling over 100% sulfuric acid 93 kilogram), 129.8 kilograms in 95% Repone K (rolling over 100%123.3 kilograms), 34.8 kilograms of 99% ammonia (rolling over 100%34.5 kilograms).Be the association agent with the alkyl tertiary amine and recycle.Through associating, replacing, operations such as regeneration are produced 147 kilograms of vitriolate of tartar, 106.8 kilograms of ammonium chlorides, the rate of recovery 97.5% of potassium, the sulfuric acid rate of recovery 96%, ammonia utilization ratio 90%.The underlying condition of present embodiment is:
1. associate
Mole ratio: H 2SO 4: R 3N=1: 1.0～2.2
Temperature of reaction: 25～100 ℃
The stirring reaction time: 0.5～4 hour
2. displacement
Mole ratio: H 2SO 4: KCL=1: 1.0～2.2
Temperature of reaction: 30～100 ℃
The stirring reaction time: 0.5～4 hour
3. regeneration
Mole ratio: HCL: NH 3=1: 0.9～1.2
Temperature of reaction: 40～100 ℃
The stirring reaction time: 0.5～4 hour
The potassium product quality:
The project quality index
Vitriolate of tartar (K 2SO 4) content 95.5%
Potassium oxide (K 2O) content 51.6%
Muriate (CL) 0.5%
Moisture 3.0%
The ammonium chloride product quality:
The project quality index
Nitrogen content (N) 24%
Moisture 4%
Embodiment 2
100 kilograms of industrial sulphuric acids with 93% (rolling over 100% sulfuric acid 93 kilogram), 134.9 kilograms in 95% Repone K (rolling over 128.2 kilograms in 100% Repone K), 35.5 kilograms of 99% ammonia (rolling over 35.1 kilograms of 100% ammonia).Be the association agent with the alkyl tertiary amine and recycle, through preparation, form put, operation such as regeneration.Produce 151.2 kilograms of vitriolate of tartar, 103.3 kilograms of ammonium chlorides.The rate of recovery 96% of potassium, the sulfuric acid rate of recovery 98%, the main technique condition of utilization ratio 90% present embodiment of ammonia is:
1. preparation
Mole ratio: H 2SO 4: KCL=1: 1.0～2.2
Dissolving solvent temperature: 30～100 ℃
Dissolved stirring time: 0.5～4 hour
2. form and put
Mole ratio: H 2SO 4: R 3N=1: 1.0～2.2
Temperature of reaction: 30～100 ℃
The stirring reaction time: 0.5～4 hour
3. regeneration
Mole ratio: HCL: NH 3=1: 0.9～1.2
Temperature of reaction: 40～100 ℃
The stirring reaction time: 0.5～4 hour
The potassium product quality
The project quality index
Vitriolate of tartar (K 2SO 4) content 95%
Potassium oxide (K 2O) content 51.3%
Muriate (CL) 0.5% 0.5%
Moisture 3.0%
The ammonium chloride product quality
The project quality index
Nitrogen content (N) 24%
Moisture 4%

Claims (5)

1, a kind of method of producing vitriolate of tartar is characterized in that doing the association agent with alkyl tertiary amine, Repone K and sulfuric acid or sulfur waste acid is directly transformed produce vitriolate of tartar, and byproduct is an ammonium chloride.
2, the method for producing vitriolate of tartar according to claim 1, it is characterized in that sulfuric acid and alkyl tertiary amine carry out association reaction with 1: 0.9～2.6 mol ratio, temperature is 5～150 ℃, 0.1～8 hour stirring reaction time, sulfuric acid and Repone K are with the amount of 1: 1.0～3.0 mol ratios in the above-mentioned reaction gained alkyl tertiary amine vitriol, Klorvess Liquid or the Klorvess Liquid that is dissolved with vitriolate of tartar, sal enixum put into carry out replacement(metathesis)reaction in the alkyl tertiary amine vitriol, 10～120 ℃ of temperature, 0.1～8 hour stirring reaction time.
3, the method for producing vitriolate of tartar according to claim 1, it is characterized in that sulfuric acid and Repone K are with 1: 0.9～3.0 mol ratio, under 5～120 ℃ of temperature, stirred 0.1～8 hour, Repone K is dissolved in sulfuric acid and the water: sulfuric acid and alkyl tertiary amine in the above-mentioned solution of preparing are dropped in the alkyl tertiary amine with 1: 0.9～2.6 mol ratio, under 5～150 ℃ of temperature, stirred 0.1～8 hour, form and put reaction.
4, according to claim 1 or the 2 or 3 described methods of producing vitriolate of tartar, the agent that it is characterized in that associating is the hydrocarbon polymer that contains nitrogen, and its general formula is R 3N is an alkyl tertiary amine, and it has three alkyl, and each all is the alkyl with free functional group form, and the carbonatoms of alkyl is more than five or five.
5, according to claim 1 or the 2 or 3 described methods of producing vitriolate of tartar, it is characterized in that alkyl tertiary amine hydrochloride and the ammonia that is dissolved in the water or in the ammonium chloride solution carry out regenerative response, the hydrogenchloride in the alkyl tertiary amine hydrochloride and the mol ratio of ammonia are 1: 0.8～1.4, under 10～150 ℃ of temperature, stirring reaction 0.1～8 hour, the alkyl tertiary amine after the regeneration recycles.
CN 88105025 1988-02-11 1988-02-11 Method of making potassium sulfate Expired CN1013100B (en)

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Application Number Priority Date Filing Date Title
CN 88105025 CN1013100B (en) 1988-02-11 1988-02-11 Method of making potassium sulfate

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Application Number Priority Date Filing Date Title
CN 88105025 CN1013100B (en) 1988-02-11 1988-02-11 Method of making potassium sulfate

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CN1034906A true CN1034906A (en) 1989-08-23
CN1013100B CN1013100B (en) 1991-07-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1125776C (en) * 1999-01-27 2003-10-29 青岛科技大学 Metathesis process for producing potassium sulfate in ammonia/water medium

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1125776C (en) * 1999-01-27 2003-10-29 青岛科技大学 Metathesis process for producing potassium sulfate in ammonia/water medium

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CN1013100B (en) 1991-07-10

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