CN1032804C - Method for prodn. of potassium sulphate using ammonium sulphate and potassium chloride - Google Patents
Method for prodn. of potassium sulphate using ammonium sulphate and potassium chloride Download PDFInfo
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- CN1032804C CN1032804C CN 93111750 CN93111750A CN1032804C CN 1032804 C CN1032804 C CN 1032804C CN 93111750 CN93111750 CN 93111750 CN 93111750 A CN93111750 A CN 93111750A CN 1032804 C CN1032804 C CN 1032804C
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Abstract
The present invention relates to a method for preparing potassium sulfate by ammonium sulfate and potassium chloride, which belongs to the class of inorganic chemistry and relates to the technical field of preparing potassium sulfate by the double decomposition of ammonium sulfate. Ammonium sulfate, potassium chloride, cyclic mother solution and cleaning solution are mixed and react under certain conditions to obtain a potassium sulfate coarse product by filtration, and a potassium sulfate refined product can be obtained after the potassium sulfate coarse product is washed by water. Ammonium chloride can be separated out by that the filtrate is crystallized by cooling, and the mother solution in which ammonium oxide is separated out and the cleaning solution can be returned to be recycled. The present invention has the advantages of simple flow, easy operation, high use rate of potassium, the recycle of the mother solution, and no pollution of three wastes. The potassium sulfate product can reach the first-class product standard of a potassium sulfate first-class product for agricultural use.
Description
The present invention is a kind of production technology of relevant vitriolate of tartar, particularly a kind of method of producing vitriolate of tartar with ammonium sulfate and Repone K.
Vitriolate of tartar is a kind of important chlorideless potassic fertilizer, be used for cash crop such as tobacco, citrus, grape in a large number, it is again a kind of basic chemical raw materials simultaneously, is used for glass, dye well pharmaceutically, China's one annual requirement is about more than 50 ten thousand tons, basic at present all dependence on import.
The production method of vitriolate of tartar has a variety of, and utilizes ammonium sulfate, Repone K to transform the advantage that vitriolate of tartar has the easy row of raw material of producing, thereby is subjected to the attention of various countries.
US1922682 has proposed ammonium sulfate and solid potassium chloride are put into the ammonium chloride decomposition volatilization that High Temperature Furnaces Heating Apparatus makes generation, discharges the product vitriolate of tartar from High Temperature Furnaces Heating Apparatus continuously, and evaporable ammonia reclaims with lime, generates ammonium sulfate with sulfuric acid again.This method characteristics are that product vitriolate of tartar purity is higher, cause environmental pollution but that its defective is technical process is long, cost is high, corrosion is big, reclaim ammonia.
DE1902738 has introduced with ammonium sulfate, Repone K and has contained the reaction of ammonia mother liquor on a small quantity and generated mixture and the mother liquor that contains ammonium chloride, vitriolate of tartar, with extraction agent ammonium chloride is extracted from mixture then, these method characteristics are side product sodium chloride purity height but product vitriolate of tartar purity is not high, but also will consume a large amount of extraction agents.
DE946434, DE2142114, CA1197663 and JP7322907 have introduced respectively with ammonium sulfate liquor and Repone K and have carried out conversion reaction under the methyl alcohol situation and produce vitriolate of tartar feeding ammonia or add, these class methods are from coming down to utilize the existence of ammonia or METHANOL MEDIUM to change the easy and ammonium sulfate formation sosoloid characteristics of product vitriolate of tartar, improved vitriolate of tartar purity, but its weak point, the one, need set up ammonia, methanol recovery system and cause that investment is big, cost is high: the 2nd, environmental pollution is serious.
FR765282, JP7220457 has introduced the lower thick vitriolate of tartar of first the first step reaction generation vitriolate of tartar content in the aqueous solution with excess sulfuric acid ammonium and Repone K respectively, the thick vitriolate of tartar that produces with the certain Klorvess Liquid and the first step carries out the reaction of second step more then, the ammonium sulfate and the Repone K that form sosoloid in the thick vitriolate of tartar are fully transformed again, potassium oxide reaches more than 50% in the product vitriolate of tartar thereby make, but owing to adopt the second one-step chlorination aqueous solutions of potassium to add, the vitriolate of tartar productive rate is reduced greatly, and cause the mother liquor surplus with a large amount of addings of rate of water added, unnecessary mother liquor can only discharge, and is unreasonable economically.
The 6th page of domestic " chemical fertilizer industry " 1987 the 1st phase reported employing ammonium sulfate and Repone K generates vitriolate of tartar at 60 reactant aqueous solutions, filtering separation gets product vitriolate of tartar and mother liquor, then this mother liquor is carried out evaporate to dryness and get the side product sodium chloride mixed fertilizer, this method technology is simple, reduced investment, but energy consumption is very high.And mother liquor do not recycle, potassium transformation efficiency only 60%.
The objective of the invention is in order to overcome many defectives that above-mentioned ammonium sulfate and Repone K transform potassium sulfate making, further consider that again present China import vitriolate of tartar has 98% all to be used for the agricultural no chlorine fat material reality of work of mixing.Proposed that a flow process is simple, processing ease, potassium utilization ratio height, energy-conservation, Recycling Mother Solution is used, non-environmental-pollution produce the unique production method of vitriolate of tartar.
Technical solution of the present invention is to adopt a step wet method, generates vitriolate of tartar and ammonium chloride with dissolving with powdery Repone K after the solid ammonium sulfate dissolving again and carrying out replacement(metathesis)reaction under certain condition earlier, and its reaction formula is:
The reaction after product separates according to its different solubility of differing temps, at first under the higher situation of temperature, carry out liquid-solid separation, vitriolate of tartar enters solid phase, and refining through water washing, the control water temperature and the water yield make and meet first grade K in the ZBG21006-89 potassium sulfate for agricultural use product standard
2The vitriolate of tartar of O 〉=45%, Cl≤2.5%, potassium is converted to potassium oxide content greater than 47% in the vitriolate of tartar, and cl content is less than 2.5% in the vitriolate of tartar, and the liquid phase after the liquid-solid separation is that mother liquor I is with NH
4Cl is a main body, adopt the cooling crystallisation by cooling to isolate the ammonium chloride solid phase, the most retrieval system of isolating after the ammonium chloride solid phase of mother liquor II is dissolved ammonium sulfate with the front washings again with Repone K is proceeded replacement(metathesis)reaction, and mother liquor II evaporates and draws solid ammonium chloride on a small quantity.
Technical process block diagram of the present invention as shown in Figure 1, all operations all carries out under normal pressure.(referring to Fig. 1)
1, earlier ammonium sulfate solids and circulating mother liquor II, washings (were obtained the circulation from last time, if when testing for the first time, the artificial preparation of employing) less water is carried out normal temperature and is mixed in container, stirring is with this mixture rising temperature for dissolving, when treating that temperature rises to 60～80 ℃, add the Repone K powder that has been crushed to 0.1～1 mm particle size again, and constantly stir.
2, in 60～80 ℃ replacement(metathesis)reaction is carried out in above-mentioned mixed liquor insulation, and continue to stir, the reaction times is 30～90 minutes, after question response finishes, precipitation is also carried out vacuum filtration and is separated the solid-liquid phase, and solid phase is thick vitriolate of tartar, and liquid phase is separated out the ammonium chloride solid phase for mother liquor I sends to crystallisation by cooling.
3, separation being made thick vitriolate of tartar solid phase water washs, water temperature is controlled at 20～90 ℃ of washing water consumptions, and water consumption is 1: 1～2 (weight ratios) with the ratio of thick vitriolate of tartar, and washings is separated with smart vitriolate of tartar, washings recycles, and POV potassium drying makes finished product.
4, will separate the mother liquid obtained I cooling of thick vitriolate of tartar crystallisation by cooling and separate out the ammonium chloride solid phase, cooling temperature is controlled at 10～40 ℃, then vacuum filtration separate chloride solid and mother liquor II, the mother liquor II overwhelming majority recycles, chloride solid carries out dry byproduct cooling ammonium chloride.
5, above-mentioned mother liquor II small part is sent vaporizer, and evaporation is anhydrated, and makes byproduct evaporate to dryness ammonium chloride.In separation, process of cooling, the part mechanical loss is arranged.During replacement(metathesis)reaction, the portion water evaporation is arranged.
Fig. 1 is a kind of technical process block diagram of producing the vitriolate of tartar method with ammonium sulfate and Repone K of the present invention.
Fig. 2 and Fig. 3 are the technical process block diagram of the embodiment of the invention 1 and embodiment 2.Mark the weight rate (gram) of each logistics among the figure.
Further illustrate the flow operations process below in conjunction with two embodiment:
Embodiment 1, referring to Fig. 2.
For convenience of explanation, we are painted on the operation steps of embodiment 1 on Fig. 2, the weight of various materials in operation is listed in also on Fig. 2 that (numeral in the figure bracket is the weight of material in the experiment, unit: gram), their Chemical Composition content is listed on the table 1, and used ammonium sulfate is Nanjing Steel ﹠ Iron Plant's product.
With 86 gram ammonium sulfate and artificial preparation mother liquor II 300 grams, washings 122 grams (composition sees Table 1), add in 800 ml beakers at 20 ℃, add 10 gram water again, this mixed solution placed have electric heater unit, have in the glass water-bath of whipping appts and carry out rising temperature for dissolving, when treating that temperature reaches 60 ℃, adding granularity in this solution is 0.5 millimeter Repone K, 95 grams, and replacement(metathesis)reaction is carried out in insulation.During metathesis, Yin Wendu high evaporation water outlet 28.17 grams.
React after 1 hour, insulation sedimentation 10 minutes, incline and clear liquid, remaining slurry carries out solid-liquid separation under vacuum filtration, get thick vitriolate of tartar 125 grams, mechanical loss 34.3 grams, merge altogether filtrate and sedimentation clear liquid to such an extent that 425 grams (claiming mother liquor I) mix for next stage cooling usefulness, add 70 ℃ of hot water, 100 grams and wash in 125 gram solids crude vitriolate of tartar, suction filtration is isolated washing 134 grams, smart vitriolate of tartar 91 grams.
Crystallization was separated out ammonium chloride and is carried out the vacuum filtration separation when the mother liquid obtained I425 gram of solid-liquid separation after the replacement(metathesis)reaction was cooled to 20 ℃, get filtrate 354 grams, solid ammonium chloride 54 grams, mechanical loss 17 grams, 300 grams return the front among this filtrated stock II, be used to dissolve ammonium sulfate and Repone K, remaining 54 gram mother liquor II heating evaporations are to doing to such an extent that evaporate to dryness post chlorization ammonium 19.2 restrains.Water evaporation 34.8 grams.
Embodiment 2: referring to Fig. 3.
The operation steps of embodiment 2 is identical with embodiment 1, and each weight of material is seen Fig. 3, and the experimental data of various materials is appointed and is listed in the bracket, mother liquor II wherein, and washings is all from a last circulation output.The Chemical Composition content of the various materials of present embodiment is listed in the table 2.
With 86 gram ammonium sulfate and last circulation output mother liquor II300 gram, washing lotion 122 grams mix in the time of 30 ℃, add 10 gram water again, this mixed solution is inserted rising temperature for dissolving in the glass water-bath that has electrically heated and whipping appts, when treating that temperature reaches 80 ℃, adding granularity in this solution is 0.1 millimeter Repone K, 95 grams, the insulation replacement(metathesis)reaction.Automatically evaporate 28.4 grams that anhydrate this moment.
React after 40 minutes, insulation sedimentation 20 minutes, incline and clear liquid, remaining slurry vacuum filtration separates to such an extent that solids crude vitriolate of tartar 138 restrains, mechanical loss 16.6 gram merges altogether filtrate and sedimentation clear liquid to such an extent that 430 grams (claiming mother liquor I) mix for next stage cooling usefulness, restrains to 50 ℃ of hot water of 138 gram solids crude vitriolate of tartar addings 100 and washs, suction filtration is isolated washings 144 grams, smart vitriolate of tartar 94 grams.
Ammonium chloride was separated out in crystallization when mother liquor I 430 gram of solid-liquid separation after the replacement(metathesis)reaction was cooled to 25 ℃, and carry out vacuum filtration and separate, get filtrate mother liquor II 350 grams, solid ammonium chloride 57 grams, mechanical loss 23 grams, 300 grams return the front among this mother liquor II, are used to dissolve ammonium sulfate and Repone K, and remaining 50 gram mother liquor II heating evaporations get ammonium chloride 17.4 grams.Water evaporation 32.6 grams.
By embodiment 1 and embodiment 2 as can be seen, advantage of the present invention is that available ammonium sulfate and Repone K are made qualified agricultural potassium sulfate first grade.
Present embodiment 1 and 2 gained vitriolate of tartar content are converted into potassium oxide difference 47.50% and 47.05%; Change among the embodiment 1 that the potassium oxide transformation efficiency is 73.20% in the product vitriolate of tartar over to, embodiment 2 reaches 74.9%, and this is than the domestic ammonium sulfate that utilizes, and Repone K transforms the yield average 60% of producing vitriolate of tartar and wants high, i.e. potassium utilization ratio height; The present invention simultaneously adopts crystallisation by cooling to separate out ammonium chloride and saves a large amount of energy consumptions than domestic employing method of evaporation recovery ammonium chloride; The present invention's solution in whole technology basically forms closed cycle, so three-waste free discharge.Flow process of the present invention is simple, processing ease, adopts the stirring reaction under the normal pressure, conventional liquid-solid separation, and the product vitriolate of tartar all can be used for having important social benefit and economic benefit in the different demand fertilizer with byproduct ammonium chloride.(table is seen the literary composition back)
The Chemical Composition content (wt%) of various materials among table 1 embodiment 1 (Fig. 2)
| The Chemical Composition name of material | ????KCl | ????NH 4Cl | (NH 4) 2SO 4 | ????K 2SO 4 | ||
| Raw material | Repone K | ????99.32 | ||||
| Ammonium sulfate | ????99.0 | |||||
| Product | Vitriolate of tartar | ????3.38 | ????8.95 | ????87.73 | ||
| Cooling ammonium chloride | ????5.08 | ????73.71 | ????20.14 | |||
| Evaporate to dryness ammonium chloride | ????16.68 | ????58.87 | ????24.51 | |||
| Intermediate material | Mother liquor I | ????14.30 | ????23.24 | ????5.29 | ||
| Mother liquor II | Drop into * * | ????11.74 | ????18.12 | ????4.42 | ||
| Output | ????12.37 | ????17.43 | ????5.74 | |||
| Washings | Drop into * * | ????4.87 | ????12.88 | ????11.31 | ||
| Output | ????5.14 | ????12.76 | ????12.72 | |||
This is experiment for the first time for *, and these materials are artificial preparation.
The Chemical Composition content (wt%) of various materials among table 2 embodiment 2 (Fig. 3)
| The Chemical Composition name of material | ????KCl | ????NH 4Cl | (NH 4) 2SO 4 | ????K 2SO 4 | ||
| Raw material | Repone K | ????99.32 | ||||
| Ammonium sulfate | ????99.0 | |||||
| Product | Vitriolate of tartar | ????3.13 | ????9.64 | ????86.90 | ||
| Cooling ammonium chloride | ????4.81 | ????74.51 | ????19.87 | |||
| Evaporate to dryness ammonium chloride | ????21.58 | ????56.35 | ????22.05 | |||
| Intermediate material | Mother liquor I | ????13.89 | ????23.10 | ????6.43 | ||
| Mother liquor II | Drop into | ????11.59 | ????18.14 | ????4.96 | ||
| Output | ????12.37 | ????17.62 | ????4.81 | |||
| Washings | Drop into | ????8.52 | ????16.01 | ????8.56 | ||
| Output | ????7.94 | ????13.18 | ????9.97 | |||
Claims (1)
1, a kind of method of producing vitriolate of tartar with ammonium sulfate and Repone K, it is characterized in that earlier the ammonium sulfate solids circulating mother liquor, washings, less water is carried out mixed dissolution, intensification adds 0.1-1 millimeter powdery Repone K and carries out stirring and dissolving and carried out under 60-80 ℃ replacement(metathesis)reaction 30-90 minute under 60-80 ℃ of temperature, after finishing, question response carries out the liquid-solid phase filtering separation, the thick vitriolate of tartar of solid phase washs to such an extent that POV potassium solid and washings water consumption are 1: 1～2 with thick vitriolate of tartar weight ratio with 20-90 ℃ of water, the filtrate of filtering thick vitriolate of tartar gained cools to 10-40 ℃ of crystallisation by cooling and separates out chloride solid, and the washings of isolating mother liquor and the thick vitriolate of tartar of washing behind the ammonium chloride returns and recycles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93111750 CN1032804C (en) | 1993-09-23 | 1993-09-23 | Method for prodn. of potassium sulphate using ammonium sulphate and potassium chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93111750 CN1032804C (en) | 1993-09-23 | 1993-09-23 | Method for prodn. of potassium sulphate using ammonium sulphate and potassium chloride |
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| CN1100699A CN1100699A (en) | 1995-03-29 |
| CN1032804C true CN1032804C (en) | 1996-09-18 |
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| CN106315627A (en) * | 2016-08-12 | 2017-01-11 | 宜昌富升化工有限公司 | Production technology of potassium sulfate |
| CN107247470B (en) * | 2017-06-19 | 2020-01-10 | 青海盐湖工业股份有限公司 | Automatic control system for repulping and washing in potash fertilizer production |
| CN107934994A (en) * | 2018-01-11 | 2018-04-20 | 辽宁津大肥业有限公司 | A kind of preparation method of potassium sulfate |
| CN108249460A (en) * | 2018-01-13 | 2018-07-06 | 安徽金禾实业股份有限公司 | In a kind of Sucralose and the processing method of press filtration workshop section ammonium chloride waste residue |
| CN111520975A (en) * | 2020-06-02 | 2020-08-11 | 湖南省湘衡盐化有限责任公司 | Industrial salt drying system and method |
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