CN114590820A - Purification method of potassium-containing ammonium chloride - Google Patents
Purification method of potassium-containing ammonium chloride Download PDFInfo
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- CN114590820A CN114590820A CN202210233973.4A CN202210233973A CN114590820A CN 114590820 A CN114590820 A CN 114590820A CN 202210233973 A CN202210233973 A CN 202210233973A CN 114590820 A CN114590820 A CN 114590820A
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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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Abstract
The invention discloses a purification method of potassium-containing ammonium chloride, which comprises the following steps: s1, carrying out secondary crystallization on ammonium chloride produced by potassium nitrate to obtain industrial ammonium chloride with ignition residue less than 0.12%, S2, carrying out third crystallization on the industrial ammonium chloride to obtain ammonium chloride with ignition residue less than 0.02%, S3, dissolving the ammonium chloride after the third crystallization, adding a complexing agent, and carrying out fourth crystallization to obtain a high-quality ammonium chloride product with ignition residue less than 0.005%, wherein the complexing agent is ammonium tartrate, and is added into a solution before ammonium chloride crystallization to form a chelate with potassium ions during recrystallization to destroy the formation of potassium chloride and ammonium chloride double salt, and the ignition residue of the recrystallized ammonium chloride product is reduced by 5-10 times, so that the requirement of producing a reagent product by using potassium-containing ammonium chloride is met, the method is convenient to popularize, the purification cost can be reduced, and the purification efficiency is improved.
Description
Technical Field
The invention relates to the field of ammonium chloride production, in particular to a purification method of potassium-containing ammonium chloride.
Background
The ammonium chloride is mainly used for refining batteries, electroplating, welding electrode production, dyeing and weaving, casting, medicine, flocking, fluff, fertilizers, chemical intermediates, rare and precious metals and the like, has high requirement on the purity of the ammonium chloride, can influence the use effect under the condition of insufficient purity, is mainly produced in the chlor-alkali industry at present, has the impurities of sodium as the main impurity, is generally obtained by a washing or recrystallization method, but can produce a large amount of potassium-containing ammonium chloride when ammonium nitrate is used for producing chlorine-free fertilizers for tobacco chlorine-avoiding crops, and because the radius of ammonium root is 143pm and is close to the radius of potassium ion (133pm) and rubidium ion (149pm), the ammonium salt is often isomorphous with the potassium salt and rubidium salt to form a complex salt. The conventional recrystallization method is adopted, the high-quality ammonium chloride product is difficult to obtain, so the ammonium chloride product can only be used as a fertilizer with extremely low value, the potassium-containing ammonium chloride is purified, and the currently adopted methods comprise an ion exchange method, octadeca-crown-6 complex potassium, an ammonium chloride sublimation method and the like. Because the ion exchange potentials of ammonium and potassium are similar, qualified products are difficult to obtain at low cost on an industrial scale; the octadeca-crown ether-6 complex potassium is theoretically feasible, but the industrial production is difficult to realize; the sublimation energy consumption of the ammonium chloride is high, the operation environment is severe, and the large-scale production is not ideal. Theoretically, sodium tetraphenylborate is an effective reagent for precipitating potassium, and the principle cannot be used in large-scale production due to cost, so that a purification method of potassium-containing ammonium chloride is urgently needed.
Disclosure of Invention
Aiming at the problems, the invention provides a purification process of potassium-containing ammonium chloride, which has the advantages of good purification efficiency, low purification cost and popularization.
The technical scheme of the invention is as follows:
a method for purifying potassium-containing ammonium chloride comprises the following steps:
s1, dissolving the ammonium chloride byproduct of potassium nitrate by using mother liquor, sequentially carrying out primary recrystallization and secondary recrystallization until the ignition residue of the product is less than 0.12%, and drying the crystal by spin-drying to obtain industrial-grade ammonium chloride;
s2, dissolving industrial-grade ammonium chloride by using the mother liquor, and recrystallizing for the third time until the ignition residue of the product is less than 0.02%;
s3, dissolving and heating industrial ammonium chloride with ignition residue less than 0.02% by using pure water, adding ammonium tartrate, and performing fourth recrystallization until ignition residue of the product is less than 0.005%;
s4, drying the product with the burning residue less than 0.005 percent to obtain the purified ammonium chloride product.
In the S1, the ammonium chloride as the potassium nitrate byproduct is dissolved with the mother liquor at the temperature of 90-100 ℃.
In the S2, industrial-grade ammonium chloride and mother liquor are dissolved at the temperature of 90-100 ℃.
In the S3, the dissolving and heating temperature of pure water is 80-90 ℃, and the ratio of the pure water to the ammonium tartrate is 1000/4-1000/6.
The mother liquor after the second recrystallization can be recycled for use in the first recrystallization, the mother liquor after the third recrystallization can be recycled for use in the second recrystallization, and the mother liquor after the fourth recrystallization can be recycled for use in the third recrystallization.
The mother liquor after the first recrystallization can be used for preparing ammonium tartrate in the fourth recrystallization.
The beneficial effects of the invention are:
when the burning residue is below 0.2 percent and contains potassium ammonium chloride for recrystallization, ammonium tartrate is added for reaction, the ammonium tartrate and potassium ions form a chelate, the formation of potassium chloride and ammonium chloride double salt can be damaged, the burning residue of the recrystallized ammonium chloride product is reduced by 5-10 times, the requirement of producing a reagent product by using the potassium ammonium chloride is met, the product can reach the high-grade pure index of GB/T658-2006 chemical reagent ammonium chloride, the method can be effectively popularized, the process is simple, and the purification cost is low.
Drawings
FIG. 1 is a process flow diagram of a method for purifying potassium-containing ammonium chloride according to an embodiment of the present invention.
Detailed Description
The embodiments of the present invention will be further described with reference to the accompanying drawings.
Example (b):
as shown in fig. 1, a method for purifying potassium-containing ammonium chloride comprises the following steps:
s1, dissolving 350-360kg of ammonium chloride, which is an by-product of potassium nitrate, in 1000L of mother liquor at 90-100 ℃, cooling, then performing primary recrystallization and secondary recrystallization until the ignition residue of the product is less than 0.12%, and spin-drying and drying the crystals to obtain industrial-grade ammonium chloride;
s2, dissolving 350-360kg of industrial ammonium chloride and 1000L of mother liquor at 90-100 ℃ for third recrystallization until the ignition residue of the product is less than 0.02 percent;
s3, dissolving 550 kg of industrial-grade ammonium chloride with ignition residue less than 0.02% by using 1000L of pure water, heating to 80-90 ℃, simultaneously adding 5kg of ammonium tartrate, adding ammonia water to be slightly alkaline (PH8-9) after dissolving, then adding 3-5kg of ammonium bicarbonate, reacting for 1h, filtering, concentrating the filtrate until a crystallization film appears, cooling for crystallization, throwing out crystals until the ignition residue of the product is less than 0.005%;
s4, drying the product with the ignition residue less than 0.005% at the temperature of 100 ℃ and 105 ℃ to obtain the purified ammonium chloride product.
The mother liquor after the second recrystallization may be recycled to be used in the first recrystallization, the mother liquor after the third recrystallization may be recycled to be used in the second recrystallization, and the mother liquor after the fourth recrystallization may be recycled to be used in the third recrystallization.
After tartrate is removed by chlorine type anion resin, the mother liquor after the first recrystallization returns to a potassium nitrate production system, the chlorine type resin is saturated and regenerated into the chlorine type anion resin by hydrochloric acid, the regenerated chlorine type resin is used for separating a regenerant in the first recrystallization, and the regenerated liquid is neutralized into an ammonium chloride solution containing tartrate by ammonium bicarbonate and is used for supplementing the regenerant for the fourth recrystallization.
The breaking-complexing agent is ammonium tartrate, and usually, in the ammonium chloride by-product for producing potassium nitrate by using ammonium nitrate, the ignition residue (mainly potassium salt) is 3.0-3.5%. In the analysis, the ammonium chloride and the sulfuric acid are burnt at high temperature to obtain burning residues, the burning residues mainly comprise metal sulfate, potassium in the ammonium chloride and the sulfuric acid are actually converted into potassium sulfate, and the potassium is detected by the atomic absorption through the same sample. The project thus examined the purity of the product in terms of the value of the residue on ignition in the product. In order to make the product reach the high-grade standard of the reagent, the ignition residue value of the product is required to be less than 0.005%, a recrystallization mode is adopted, the ammonium chloride byproduct is recrystallized once, the ignition residue can be reduced to be less than 0.6%, and the reduction of recrystallization impurities is reduced by 3-5 times. The recrystallization again also satisfies the experience of 3-5 times reduction of recrystallization impurities. The burning residue can be reduced to below 0.2%. But when the potassium-containing ammonium chloride with the ignition residue of about 0.1 percent is recrystallized, the ignition residue of the product is almost unchanged, which is probably the reason for forming a double salt between potassium chloride and ammonium chloride, ammonium tartrate is taken as a breaker, when the potassium-containing ammonium chloride with the ignition residue of less than 0.2 percent is recrystallized, the ammonium tartrate is added into a solution before ammonium chloride crystallization to form a chelate with potassium ions, the formation of the potassium chloride and ammonium chloride double salt is broken, the ignition residue of the recrystallized ammonium chloride product is reduced by 5 to 10 times, the requirement of producing a reagent product by using the potassium-containing ammonium chloride is met, and the product can reach the GB/T658-2006 chemical reagent ammonium chloride superior grade pure index.
The addition of ammonium tartrate to potassium-containing ammonium chloride is understood to mean that potassium ions form, with tartaric acid ions, a low-solubility substance of potassium bitartrate:
K++C4H5O6-→KC4H5O6
the potassium ions are beam-bound to the bitartrate ions, reducing the concentration of free potassium ions in the solution and purifying the ammonium chloride during recrystallization. This is similar to the principle of potassium nitrate production by adding potassium chloride to ammonium nitrate solution, where ammonium ions and chloride ions form low-solubility ammonium chloride and potassium nitrate is purified.
NH4 ++Cl-→NH4Cl
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (6)
1. A method for purifying potassium-containing ammonium chloride is characterized by comprising the following steps:
s1, dissolving the ammonium chloride byproduct of potassium nitrate by using mother liquor, sequentially carrying out primary recrystallization and secondary recrystallization until the ignition residue of the product is less than 0.12%, and drying the crystal by spin-drying to obtain industrial-grade ammonium chloride;
s2, dissolving industrial ammonium chloride by using the mother liquor, and carrying out third recrystallization until the ignition residue of the product is less than 0.02%;
s3, dissolving and heating industrial ammonium chloride with ignition residue less than 0.02% by using pure water, adding ammonium tartrate, and performing fourth recrystallization until ignition residue of the product is less than 0.005%;
s4, drying the product with the burning residue less than 0.005 percent to obtain the purified ammonium chloride product.
2. The method for purifying potassium-containing ammonium chloride as claimed in claim 1, wherein in the S1, the ammonium chloride produced by potassium nitrate is dissolved in the mother liquor at 90-100 ℃.
3. The method for purifying ammonium chloride containing potassium according to claim 1, wherein in the S2, the industrial-grade ammonium chloride is dissolved with the mother liquor at 90-100 ℃.
4. The method for purifying ammonium chloride containing potassium according to claim 1, wherein the temperature for dissolving and heating pure water in S3 is 80-90 ℃, and the ratio of pure water to ammonium tartrate is 1000/4-1000/6.
5. The method for purifying potassium-containing ammonium chloride as claimed in claim 1, wherein the mother liquor after the second recrystallization can be recycled to be used in the first recrystallization, the mother liquor after the third recrystallization can be recycled to be used in the second recrystallization, and the mother liquor after the fourth recrystallization can be recycled to be used in the third recrystallization.
6. The method for purifying ammonium chloride containing potassium according to claim 1, wherein the mother liquor after the first recrystallization can be used for preparing ammonium tartrate in the fourth recrystallization.
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| CN1341558A (en) * | 2001-09-26 | 2002-03-27 | 山西兴安化学工业(集团)有限责任公司 | Method for preparing potassium sulfate |
| US20110044879A1 (en) * | 2006-03-22 | 2011-02-24 | Soos Janos Gyoergy | Process for the treatment and purification of dangerous wastes containing ammonium salts, particularly ammonium chloride, derived from pharmaceutical and chemical technologies |
| CN103588223A (en) * | 2013-11-21 | 2014-02-19 | 浙江大洋生物科技集团股份有限公司 | Method for producing high-purity ammonium chloride through multistage flash evaporation, cooling and continuous crystallization |
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| WO2022023886A1 (en) * | 2020-07-28 | 2022-02-03 | Edale S.R.L. | Process for the production of potassium sulphate based fertilizers |
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