CN112142068A - Method for producing high-purity ammonium chloride from industrial-grade ammonium chloride - Google Patents
Method for producing high-purity ammonium chloride from industrial-grade ammonium chloride Download PDFInfo
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 title claims abstract description 337
- 235000019270 ammonium chloride Nutrition 0.000 title claims abstract description 162
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 42
- 238000002386 leaching Methods 0.000 claims abstract description 20
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000011282 treatment Methods 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims description 32
- 239000003456 ion exchange resin Substances 0.000 claims description 13
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910001414 potassium ion Inorganic materials 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims 2
- 229910001424 calcium ion Inorganic materials 0.000 claims 2
- 239000012535 impurity Substances 0.000 claims 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims 2
- 239000012487 rinsing solution Substances 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 29
- 239000000126 substance Substances 0.000 abstract description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011591 potassium Substances 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003729 cation exchange resin Substances 0.000 abstract description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011777 magnesium Substances 0.000 abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 229910052700 potassium Inorganic materials 0.000 abstract description 5
- 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 abstract description 4
- 239000011734 sodium Substances 0.000 abstract description 4
- 239000003337 fertilizer Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a method for producing high-purity ammonium chloride from industrial-grade ammonium chloride, which comprises the steps of taking the industrial-grade ammonium chloride as a raw material, removing metal ions such as potassium, sodium, magnesium, iron and the like through twice crystallization and leaching by utilizing different solubilities and different changes of the solubilities of the ammonium chloride and other metal chloride at different temperatures, and then heating and concentrating by steam to obtain the ammonium chloride with higher purity. And purifying the treated ammonium chloride again by using cation exchange resin to ensure that the content of metal ions in the ammonium chloride is lower than 100ppb, thereby achieving the grade applicable to electronic-grade products. According to the treatment method disclosed by the invention, the yield of the ammonium chloride can reach 80-90%, no new chemical substance is introduced in the treatment process, no new pollutant is brought to the original ammonium chloride system, meanwhile, the collected leacheate and the filtered mother liquor are collected, finally, the low-grade ammonium chloride is obtained and used in industries such as fertilizers, and the resources are maximally applied.
Description
Technical Field
The invention relates to a purification method of industrial-grade ammonium chloride, in particular to a method for removing metal ions of the industrial-grade ammonium chloride.
Background
Ammonium chloride is used as an important nitrogen source, has important application in agriculture, and has low requirements on metal ions. However, in the application of the electronic industry, metal ions contained in the electronic industry, such as potassium, sodium, calcium, magnesium, iron and the like, have great influence on products in the applied industry.
At present, methods for removing metal ions from ammonium chloride include organic solvent extraction, chemical reaction by adding other chemicals, and ion exchange.
Organic solvent extraction and reaction by adding other chemical substances to remove metal ions in ammonium chloride. The method introduces a new chemical substance, easily causes pollution of the original system, and has difficult collection and treatment of the waste water after reaction and larger environmental protection pressure.
The ion exchange method mainly removes potassium and sodium ions, firstly, cation resin is treated to form ammonium resin, and a high-potassium-sodium ammonium chloride solution passes through the ammonium resin to remove the potassium and sodium ions in the solution.
The three methods not only generate waste liquid to generate certain pressure on the environment, but also the metal ions in the treated ammonium chloride still reach 50ppm or above, and the waste liquid still cannot meet the requirements in the electronic industry and cannot be directly used.
Disclosure of Invention
In order to remove metal ions in industrial ammonium chloride with high efficiency, the invention aims to provide an environment-friendly and effective metal ion removal method, firstly, chlorine-containing metal salts with different saturation solubilities in deionized water are utilized, the industrial ammonium chloride is crystallized and purified twice by a dissolving and crystallizing method, then, the metal ions in the ammonium chloride after the crystallization treatment are removed by cation exchange resin so as to further purify the ammonium chloride, and the metal ions in the ammonium chloride can be removed to be lower than 100 ppb.
A method for producing high purity ammonium chloride from technical grade ammonium chloride comprising the steps of:
(1) dissolving industrial-grade ammonium chloride in deionized water at 60-90 ℃ (preferably 80 ℃), so that the ammonium chloride can be dissolved to the maximum extent, the dissolution difference between the ammonium chloride and sodium ions is opened, the operation is convenient, the solution is saturated, a saturated ammonium chloride solution is obtained, and the solubility of the ammonium chloride at 80 ℃ is 65.6g/100 g;
(2) slowly cooling the saturated ammonium chloride solution in the step (1) to crystallize ammonium chloride;
(3) keeping the crystallization temperature of the ammonium chloride crystallized in the step (2) for filtering to obtain ammonium chloride crystals, and collecting the ammonium chloride mother liquor obtained by filtering for later treatment;
(4) leaching the ammonium chloride crystals obtained in the step (3) through leacheate to obtain ammonium chloride crystals with higher purity for later use, and collecting the leacheate to be treated; in order to wash more thoroughly, the obtained ammonium chloride crystals can be dissolved and crystallized, and then are washed again by the eluent to obtain ammonium chloride crystals with higher purity for later use, and the eluent is collected for treatment;
(5) dissolving the collected ammonium chloride crystals, continuously removing metal ions in the ammonium chloride through an exchange column of cationic resin to obtain a high-purity ammonium chloride solution, and carrying out steam concentration and drying on the obtained solution to obtain high-purity ammonium chloride;
(6) and (4) concentrating the ammonium chloride mother liquor and the leacheate in the steps (3), (4) and (5) by steam, and drying to obtain an ammonium chloride product with a lower grade, wherein the ammonium chloride product can be used for products such as fertilizers.
The content of metal ions in the ammonium chloride in the step (1) is shown in table 1, sodium ions in industrial-grade ammonium chloride are more than 20000ppm, metal ions such as potassium, magnesium and calcium are more than 200ppm, and other metal ions such as iron and manganese are more than 20ppm, so that the ammonium chloride can not meet the requirements of wet electronic chemical industry.
TABLE 1 Metal ion content of technical ammonium chloride
According to the analysis of different solubilities of different metal chlorides along with the temperature, as shown in the table 2, the main component ammonium chloride solubility is increased along with the temperature, the sodium chloride solubility is less changed along with the temperature, sodium ions can be efficiently removed by a dissolving and crystallizing method, and meanwhile, part of other metals such as potassium, calcium, magnesium, aluminum, copper and the like are removed. In the step (1), 80 ℃ is preferably selected, too high temperature (such as over 100 ℃) can cause slow decomposition of ammonium chloride and reduce the yield of the ammonium chloride, and too low temperature (such as 60 ℃ can cause difficult separation due to unobvious solubility difference).
TABLE 2 solubility of different chlorides at different temperatures
And (2) slowly cooling the ammonium chloride solution at the room temperature when the temperature of the ammonium chloride solution is 80 ℃, placing the ammonium chloride solution into a low-temperature constant-temperature water bath pot when the temperature is consistent with the room temperature, cooling the ammonium chloride solution to 10-15 ℃ to slowly crystallize the ammonium chloride, then adjusting the temperature of the low-temperature constant-temperature water bath pot to 0 ℃, continuously crystallizing the ammonium chloride, and reducing the temperature step by step to stably and slowly crystallize the ammonium chloride so as to prevent the crystallization speed from being too high, and reduce the removal effect of metal ions because a large amount of metal is wrapped by crystals.
And (4) in the step (3), the crystallization temperature is kept for filtration, so that the ammonium chloride yield is prevented from being reduced due to the dissolution of the ammonium chloride caused by the temperature rise. And continuously collecting the ammonium chloride solid obtained by filtering and carrying out subsequent treatment in a sand core funnel, and collecting the ammonium chloride mother liquor in a clean container for subsequent utilization.
And (4) washing the ammonium chloride solid in the sand core funnel by using a saturated ammonium chloride solution, ice water at 0 ℃ or hydrochloric acid with the mass concentration of 36.5-37% to remove metal ions wrapped in the ammonium chloride crystal, and collecting leacheate to be treated.
And (4) leaching the solution in the step (4) at the temperature of 10-40 ℃ for 1-30 min.
Preferably, in the step (4), the leaching temperature is preferably 10-20 ℃, the leaching time is preferably 1-5 min, the leaching time is too short, the metal ions are not completely washed, the removal rate of the metal ions is affected, the leaching time is too long, partial ammonium chloride is dissolved, and the yield of the ammonium chloride is reduced.
The metal ions of the ammonium chloride product obtained by the treatments in the above steps (1) to (4) are shown in table 3.
TABLE 3 content of metal ions in crystalline ammonium chloride
The data in table 3 show that after two times of dissolution, crystallization and leaching, the removal rate of sodium and potassium ions in ammonium chloride is high, and other metal ions are less than 100ppb, but for the wet electronic chemical industry, the treatment is still needed to continuously reduce the content of the metal ions when the ammonium chloride is used.
And (5) adding ammonium chloride into 732-type hydrogen ion exchange resin to convert the cation exchange resin into ammonium type ion exchange resin, and removing metal ions in the ammonium chloride through the exchange of ammonium radicals and metal ions in the ammonium chloride, such as sodium, potassium, magnesium and the like.
Preferably, the volume ratio of the ammonium chloride to the 732-type hydrogen ion exchange resin is 1-3: 1 when the hydrogen resin is converted into the ammonium resin in the step (5).
And (4) collecting the collected ammonium chloride mother liquor and the leacheate in the step (6), and concentrating the ammonium chloride mother liquor and the leacheate through steam to obtain low-grade ammonium chloride solids.
Through the treatment of the steps, the yield of the ammonium chloride can reach 80-90%.
By the treatment of the above steps, the metal ion content in ammonium chloride is shown in table 4:
TABLE 4 content of metal ions in high-purity ammonium chloride
The invention has the advantages that:
(1) according to the method, the ammonium chloride crystals are leached by adopting saturated ammonium chloride, so that the dissolution of the ammonium chloride crystals caused in the hot water washing process can be reduced, the collected mother liquor is still an ammonium chloride solution, the ammonium chloride solution can be collected, concentrated and used as a fertilizer and the like after being dried, the generation of byproducts is reduced, the environmental protection pressure is reduced, and the resources are utilized to the maximum extent.
(2) The method of the invention deeply exchanges metal ions in the ammonium chloride by passing the ammonium chloride which is crystallized and washed twice through ammonium type ion exchange resin, can remove the content of the metal ions to be lower than 100ppb, and can be directly applied to the wet electronic chemical industry.
(3) The method of the invention does not introduce new chemical substances in the treatment process and does not bring new pollutants to the original ammonium chloride system.
(4) The method disclosed by the invention is simple in process flow and easy to realize, the yield of ammonium chloride can reach 80-90%, and the method can be widely applied to industrial production.
Detailed Description
The present invention will be described in detail with reference to specific examples, which are provided for illustration and are not intended to limit the scope of the invention.
Example 1
(1) Weighing 800g of deionized water, weighing 524.8g of industrial-grade ammonium chloride according to the solubility of the ammonium chloride at 80 ℃, putting a beaker filled with the deionized water and the ammonium chloride in a constant-temperature water bath kettle, heating to 80 ℃, and stirring continuously to completely dissolve the ammonium chloride to obtain a saturated ammonium chloride solution;
(2) slowly cooling the saturated ammonium chloride solution at room temperature to crystallize ammonium chloride, and after the temperature reaches the room temperature, continuously crystallizing the saturated ammonium chloride solution in a low-temperature constant-temperature water bath until the temperature reaches 5 ℃;
(3) filtering the ammonium chloride crystallized in the step (2) through a sand core funnel at a crystallization temperature to obtain ammonium chloride crystals, and collecting ammonium chloride mother liquor obtained by filtering for later treatment;
(4) leaching the saturated ammonium chloride solution of the ammonium chloride crystal obtained in the step (3) at the temperature of 5 ℃, wherein leaching time is 1min, and collecting the ammonium chloride crystal;
(5) slowly heating and dissolving the ammonium chloride crystals obtained in the step (4) according to the method in the step (1), then slowly cooling at room temperature to crystallize ammonium chloride, and when the temperature reaches the room temperature, putting the ammonium chloride crystals into a low-temperature constant-temperature water bath kettle to continuously cool and crystallize until the temperature reaches 5 ℃;
(6) leaching the saturated ammonium chloride solution of the ammonium chloride crystal obtained in the step (5) at the temperature of 5 ℃ for 1min, and collecting the ammonium chloride crystal;
(7) and concentrating the collected ammonium chloride crystals by adopting pure hot air, and drying to obtain the high-purity ammonium chloride.
Example 2
The procedure is as in example 1, and only the rinsing time in the steps (4) and (6) is 3 min.
Example 3
The procedure is as in example 1, except that the rinsing time in steps (4) and (6) is 5 min.
Example 4
The procedure is as in example 3, except that the crystallization temperature in step (2) is 15 ℃, and the ammonium chloride crystals in steps (4) and (6) are rinsed with a saturated ammonium chloride solution at 15 ℃.
Example 5
The procedure is as in example 3, only the crystallization temperature in step (2) is 20 ℃, and the ammonium chloride crystals in steps (4) and (6) are rinsed with a saturated ammonium chloride solution at 20 ℃.
Example 6
The procedure is as in example 3, only the ammonium chloride crystals in steps (4) and (6) are rinsed with 37% high-purity hydrochloric acid solution at 5 ℃.
Example 7
The procedure is as in example 3, only the ammonium chloride crystals from steps (4) and (6) are rinsed in ice water at 0 ℃.
Example 8
The procedure is as in example 3, except that in step (7), the collected ammonium chloride crystals are dissolved and ion-exchanged with ammonium ion exchange resin (volume ratio of 732 type hydrogen type ion exchange resin to ammonium chloride is 1:1), metal ions in ammonium chloride are continuously removed to obtain a high-purity ammonium chloride solution, and the obtained solution is subjected to steam concentration and drying to obtain high-purity ammonium chloride.
Example 9
The procedure is as in example 3, except that in step (7), the collected ammonium chloride crystals are dissolved and ion-exchanged with ammonium ion exchange resin (volume ratio of 732 type hydrogen type ion exchange resin to ammonium chloride is 2:1), metal ions in ammonium chloride are continuously removed to obtain a high-purity ammonium chloride solution, and the obtained solution is subjected to steam concentration and drying to obtain high-purity ammonium chloride.
Example 10
The procedure is as in example 3, except that in step (7), the collected ammonium chloride crystals are dissolved and ion-exchanged with ammonium ion exchange resin (volume ratio of 732 type hydrogen type ion exchange resin to ammonium chloride is 3:1), metal ions in ammonium chloride are continuously removed to obtain a high-purity ammonium chloride solution, and the obtained solution is subjected to steam concentration and drying to obtain high-purity ammonium chloride.
The indexes corresponding to the above-mentioned embodiments 1 to 10 of the present invention are shown in table 5:
TABLE 5
From the results of the above examples, it can be seen that, compared with 1min, the 5min rinsing time can rinse the metal ions to a level meeting the use requirement, and can also effectively control the rinsing amount, the content of the metal ions is higher at 1min, the content of the metal ions is lower at 5min, and the yield difference is smaller.
From the above data analysis, the metal content was changed by changing the rinsing time after two crystallization washes. Along with the extension of the leaching time, the removal rate of metal ions adhered to the surface of the crystal is increased, the cleaning time is too long, the required leaching solution amount is increased, and the environmental protection pressure is increased. The leaching time is preferably 5min, so that the metal ions can be leached to the level meeting the use requirement, and the leaching dosage can be effectively controlled. The temperature of the leaching solution is controlled to be 5-20 ℃, the temperature is too low, more power is needed to reduce the temperature of the leaching solution to an application range, the temperature is too high, partial crystals are dissolved in the leaching process, and the yield of ammonium chloride is reduced.
The ammonium chloride leached by twice crystallization is subjected to cation exchange through ammonium type resin, the content of metal ions in the ammonium chloride can be reduced to a greater extent, when the volume ratio of the ammonium chloride to the hydrogen type cation exchange resin is 2:1, the content can be below 100ppb, the yield is as high as 90.6%, the volume of the ammonium chloride is continuously increased to convert the hydrogen type cation exchange resin into the ammonium type resin, the purification effect of the ammonium chloride is not obviously improved, and the volume ratio of the ammonium chloride to the hydrogen type cation exchange resin is preferably 2: 1.
The above description of the method for producing high purity ammonium chloride from industrial grade ammonium chloride according to the present invention is given by way of illustration only, and is not intended to limit the scope of the present invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (7)
1. A method for producing high-purity ammonium chloride from industrial-grade ammonium chloride is characterized by comprising the following steps:
(1) dissolving industrial-grade ammonium chloride in deionized water at 60-90 ℃ until the solution is saturated;
(2) cooling and crystallizing the saturated ammonium chloride solution obtained in the step (1) to obtain an ammonium chloride crystal product;
(3) keeping the crystallization temperature of the ammonium chloride crystallization product obtained in the step (2) for filtering to obtain ammonium chloride crystals, and collecting the ammonium chloride mother liquor obtained by filtering for later treatment;
(4) leaching the ammonium chloride crystals obtained in the step (3) by using leacheate to obtain ammonium chloride crystals;
(5) and dissolving the collected ammonium chloride crystals again, passing through an exchange column of cationic resin, concentrating the obtained ammonium chloride solution by steam, and drying to obtain the ammonium chloride with the metal ion impurity content of less than 100 ppb.
2. The method for producing high-purity ammonium chloride from industrial-grade ammonium chloride according to claim 1, wherein the metal ion impurities in the industrial-grade ammonium chloride in step (1) comprise sodium ions, potassium ions, magnesium ions and calcium ions, wherein the content of the sodium ions is more than 20000ppm, and the content of the potassium ions, the magnesium ions and the calcium ions is more than 200ppm respectively.
3. The method for producing high purity ammonium chloride from technical grade ammonium chloride according to claim 1,
in the step (2), the saturated ammonium chloride solution is crystallized at the temperature of 0-15 ℃.
4. The method for producing high-purity ammonium chloride from industrial-grade ammonium chloride according to claim 1, wherein the step (3) is performed by suction filtration under a vacuum degree of 0.06-0.08 Mpa during filtration.
5. The method for producing high-purity ammonium chloride from industrial-grade ammonium chloride according to claim 1, wherein the leacheate in the step (4) is concentrated hydrochloric acid with the mass concentration of 36.5-37%, ice water with the temperature of 0 ℃ or saturated ammonium chloride solution.
6. The method for producing high-purity ammonium chloride from industrial-grade ammonium chloride according to claim 1, wherein the temperature of the rinsing solution in the step (4) is 10-15 ℃; the leaching time is 1-30 min.
7. The method for producing high-purity ammonium chloride from industrial-grade ammonium chloride according to claim 1, wherein the cation resin in step (5) is ammonium type ion exchange resin 732 type hydrogen type ion exchange resin, and the volume ratio of ammonium chloride to 732 type hydrogen type ion exchange resin is 1-3: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114455607A (en) * | 2022-03-08 | 2022-05-10 | 重庆工贸职业技术学院 | Purification method of industrial by-product ammonium chloride |
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