CN102826570A - Method for producing electronic-grade ammonium chloride - Google Patents
Method for producing electronic-grade ammonium chloride Download PDFInfo
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- CN102826570A CN102826570A CN2012103041131A CN201210304113A CN102826570A CN 102826570 A CN102826570 A CN 102826570A CN 2012103041131 A CN2012103041131 A CN 2012103041131A CN 201210304113 A CN201210304113 A CN 201210304113A CN 102826570 A CN102826570 A CN 102826570A
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Abstract
The invention discloses a method for producing electronic-grade ammonium chloride. The method uses agricultural ammonium chloride as raw materials, and carries out a three-stage countercurrent washing with cold ammonia mother liquor I, hot deionized water and other solvents to produce the electronic-grade ammonium chloride. The method comprises the following steps: (1) mixing the agricultural ammonium chloride in a combined-soda production and the cold ammonia mother liquor I according to a certain proportion with stirring, and washing in the first stage; (2) washing by using a circulating mother liquor I in the second stage; and (3) washing by using the hot deionized water in the third stage. The method contacts with but does not influence the combined-soda production, has advantages of simple technology, low product cost, stable quality, no pollution, and prominent environmental protection effect.
Description
Technical field
The present invention relates to the working method of industrial ammonium chloride, concrete be meant a kind of method of producing electronic-grade ammonium chloride.
Background technology
The smart ammonium novel process of integrated process, this process using secondary washing method is produced smart ammonium, and the first step is a mixing, washing, is about to agriculture ammonium chloride and the ammonia mother liquor I mixing, washing that joins in the alkali production; The second stage is the circulation method washing, promptly washs with circulating mother liquor, in circulating mother liquor, constantly adds and removes CO
3 2-And SO
4 2-HCl and BaCl
2Receive the restriction of processing condition, the smart ammonium of integrated process can only be produced the acceptable end product industrial ammonium chloride.
The process method of domestic production electronic-grade ammonium chloride has subliming method and two kinds of comprehensive removal of impurities method of purifications.
(1) subliming method is produced electronic-grade ammonium chloride: the purity of ammonia chloride that the subliming method purification obtains is very high; Basically can not detect basic metal, earth alkali metal plasma, this method production cost is too high, and energy consumption is big; Product is difficult to collect, and is not suitable for large-scale industrial production.
(2) comprehensive removal of impurities method of purification is produced electronic-grade ammonium chloride: the core process of comprehensive removal of impurities method of purification is a recrystallization, and this method production process is simple, and good product quality can be used for large-scale industrial production.But sodium content is too high in the agriculture ammonium chloride, and only the purification with recrystallization is to be difficult to meet the requirements of, and must be aided with the method for chemical subtraction, just possibly reach requirement; This method energy consumption is high simultaneously, environmental protection pressure is big.The main processes of comprehensive removal of impurities method of purification has: chemicaladditives removal of impurities, filtration, recrystallization, washing, centrifuge dehydration, oven dry and packing.
How is the high quality and low cost high yield contamination-freely produced the electronic-grade ammonium chloride product? Need constantly to explore and research.
Summary of the invention
The object of the invention is exactly a kind of high-quality, low consumption, high yield will be provided, contamination-freely produce the method for electronic-grade ammonium chloride.
Be the realization above-mentioned purpose, the method for production electronic-grade ammonium chloride provided by the invention, it is a raw material with agriculture ammonium chloride, carries out the washing of three stage countercurrents with cold ammonia mother liquor I and hot deionized water equal solvent, and then produces electronic-grade ammonium chloride, it comprises the steps:
(1) adopt the agriculture ammonium chloride that joins in the alkali production to mix agitator treating with ammonia mother liquor I; The solid-liquid volume ratio is 20-40% in mixing solutions during washing; Deliver to one again and wash the thickening of stiff device, and obtain one-level solid ammonium chloride and filtrating after washing the whizzer solid-liquid separation through one;
(2) said one-level solid ammonium chloride is delivered in two cask washings, carries out abundant agitator treating with the circulating mother liquor I as solvent, adds BaCl in the said circulating mother liquor I
2To remove SO
4 2-Deliver to two again and wash the thickening of stiff device; And obtaining secondary solid ammonium chloride and circulating mother liquor I after washing the whizzer solid-liquid separation through two, said circulating mother liquor I is back to carries out circulation cleaning in two cask washings;
(3) said secondary solid ammonium chloride is delivered in three cask washings; By deionized water and the abundant agitator treating of secondary solid ammonium chloride as the heat of solvent; Deliver to three again and wash the thickening of stiff device, and obtain three grades of solid ammonium chlorides and circulating mother liquor II after washing the whizzer solid-liquid separation through three, said circulating mother liquor II is back to carries out circulation cleaning in three cask washings; Said three grades of solid ammonium chlorides are delivered to drying oven and are carried out drying, obtain electronic-grade ammonium chloride finished product after the packing.
As preferred version, adopt the agriculture ammonium chloride that joins in the alkali production to be wet agricultural ammonium in the said step (1); The solid-liquid volume ratio is 20-40% in mixing solutions when one-level solid ammonium chloride and circulating mother liquor I are washed in the said step (2); The solid-liquid volume ratio is 20-40% in mixing solutions when secondary solid ammonium chloride and hot deionized water wash in the said step (3); Solution temperature when washing in the said step (3) is 50-60 ℃.
Further, filtrating is back to couplet alkali production system in the said step (1); Add BaCl in the said step (2)
2To remove SO
4 2-The permanent white mud that reaction generates, the liquid that behind press filtration, obtains are back to and join the alkali production system.
Among the present invention, the solid-liquid volume ratio leaves standstill after being meant and stirring in the washing beck in the mixing solutions during described the washing, and the solid volume that is settled out accounts for the per-cent of mixing solutions TV.
The invention has the advantages that:
One of which adds bariumchloride in proportion in two cleaning mother liquors, make that sulfate ion content is reduced to below the 50ppm in the ammonium chloride product, reaches the quality standard of electronic-grade ammonium chloride.
Its two, after three grades of washings, alkali metal ion content measured such as sodium in the ammonium chloride product, potassium are reduced to below the 50ppm, reach the quality standard of electronic-grade ammonium chloride.
The mother liquor and two of its three, three times washings is washed in the process mother liquor after the permanent white press filtration and is all sent back to and join the alkali production system and recycle, and reaches zero release, and environment protecting is remarkable.
Its four, dried tail gas handle to adopt the bag-type dust method, no longer adopts traditional water washing method drying process, the one, do not have the washing water discharge of dry washing tail gas, the 2nd, do not have ammonium dirt to be discharged in the atmosphere in the tail gas, thereby reached the effect of protection environment.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is made further detailed description.
Embodiment one:
As shown in the figure: in a cask washing, by joining the cold ammonia mother liquor I (cold A I) and the abundant agitator treating of agriculture ammonium chloride that the alkali production system is sent here, the solid-liquid volume ratio is 20% in the mixing solutions during washing, delivers to one again and washes the thickening of stiff device; And through one wash the whizzer solid-liquid separation after, obtain the one-level solid ammonium chloride and get into two cask washings, one washes stiff device overflowing liquid and washes separating machine filtrating after filtrate tank compiles, and returns to join the alkali production system; After first step washing spinning, its ammonium chloride master content can reach 99.0-99.2%.
In two cask washings, by circulating mother liquor I and the abundant agitator treating of one-level solid ammonium chloride, the solid-liquid volume ratio is 20% in the mixing solutions during washing, delivers to two again and washes the thickening of stiff device; And through two wash the whizzer solid-liquid separation after, obtain the secondary solid ammonium chloride and get into three cask washings, two wash stiff device overflowing liquid and two washes separating machine filtrating and returns two cask washings and recycle; Behind circulating mother liquor I circulation cleaning, its ammonium chloride master content can be increased to more than 99.3%; Part two cleaning mother liquors return couplet alkali production system behind sulfate radical.When two cleaning mother liquors are not enough, can mend clear water (primary water).
In three cask washings, by the deionized water and the abundant agitator treating of secondary solid ammonium chloride of heat, the solid-liquid volume ratio is 20% in the mixing solutions during washing, and controlling the interior temperature of charge of three cask washings is 50 ℃; Deliver to three again and wash the thickening of stiff device; And through three wash the whizzer solid-liquid separation after, obtain three grades of solid ammonium chlorides and deliver to kiln dried, obtain electronic-grade ammonium chloride finished product after the packing; Three wash stiff device overflowing liquid and three washes separating machine filtrating and returns three cask washings and recycle, and after alkalimetal ion concentration such as the sodium in three cask washings, potassium increased, part circulating mother liquor II was delivered in two cask washings, simultaneously the deionized water of supplemental heat in three cask washings; Behind third stage circulation cleaning, its ammonium chloride master content further is increased to 99.5-99.8%, and alkalimetal ion such as sodium, potassium and sulfate ion content all be reduced to below the 50ppm, reaches the quality index of electronic-grade ammonium chloride.
Embodiment two:
As shown in the figure: in a cask washing, by joining the cold ammonia mother liquor I (cold A I) and the abundant agitator treating of agriculture ammonium chloride that the alkali production system is sent here, the solid-liquid volume ratio is 30% in the mixing solutions during washing, delivers to one again and washes the thickening of stiff device; And through one wash the whizzer solid-liquid separation after, obtain the one-level solid ammonium chloride and get into two cask washings, one washes stiff device overflowing liquid and washes separating machine filtrating after filtrate tank compiles, and returns to join the alkali production system; After first step washing spinning, its ammonium chloride master content can reach 99.0-99.2%.
In two cask washings, by circulating mother liquor I and the abundant agitator treating of one-level solid ammonium chloride, the solid-liquid volume ratio is 30% in the mixing solutions during washing, delivers to two again and washes the thickening of stiff device; And through two wash the whizzer solid-liquid separation after, obtain the secondary solid ammonium chloride and get into three cask washings, two wash stiff device overflowing liquid and two washes separating machine filtrating and returns two cask washings and recycle; Behind circulating mother liquor I circulation cleaning, its ammonium chloride master content can be increased to more than 99.3%; Part two cleaning mother liquors return couplet alkali production system behind sulfate radical.When two cleaning mother liquors are not enough, can mend clear water (primary water).
In three cask washings, by the deionized water and the abundant agitator treating of secondary solid ammonium chloride of heat, the solid-liquid volume ratio is 30% in the mixing solutions during washing, and controlling the interior temperature of charge of three cask washings is 55 ℃; Deliver to three again and wash the thickening of stiff device; And through three wash the whizzer solid-liquid separation after, obtain three grades of solid ammonium chlorides and deliver to kiln dried, obtain electronic-grade ammonium chloride finished product after the packing; Three wash stiff device overflowing liquid and three washes separating machine filtrating and returns three cask washings and recycle, and after alkalimetal ion concentration such as the sodium in three cask washings, potassium increased, part circulating mother liquor II was delivered in two cask washings, simultaneously the deionized water of supplemental heat in three cask washings; Behind third stage circulation cleaning, its ammonium chloride master content further is increased to 99.5-99.8%, and alkalimetal ion such as sodium, potassium and sulfate ion content all be reduced to below the 50ppm, reaches the quality index of electronic-grade ammonium chloride.
Embodiment three:
As shown in the figure: in a cask washing, by joining the cold ammonia mother liquor I (cold A I) and the abundant agitator treating of agriculture ammonium chloride that the alkali production system is sent here, the solid-liquid volume ratio is 40% in the mixing solutions during washing, delivers to one again and washes the thickening of stiff device; And through one wash the whizzer solid-liquid separation after, obtain the one-level solid ammonium chloride and get into two cask washings, one washes stiff device overflowing liquid and washes separating machine filtrating after filtrate tank compiles, and returns to join the alkali production system; After first step washing spinning, its ammonium chloride master content can reach 99.0-99.2%.
In two cask washings, by circulating mother liquor I and the abundant agitator treating of one-level solid ammonium chloride, the solid-liquid volume ratio is 40% in the mixing solutions during washing, delivers to two again and washes the thickening of stiff device; And through two wash the whizzer solid-liquid separation after, obtain the secondary solid ammonium chloride and get into three cask washings, two wash stiff device overflowing liquid and two washes separating machine filtrating and returns two cask washings and recycle; Behind circulating mother liquor I circulation cleaning, its ammonium chloride master content can be increased to more than 99.3%; Part two cleaning mother liquors return couplet alkali production system behind sulfate radical.When two cleaning mother liquors are not enough, can mend clear water (primary water).
In three cask washings, by the deionized water and the abundant agitator treating of secondary solid ammonium chloride of heat, the solid-liquid volume ratio is 40% in the mixing solutions during washing, and controlling the interior temperature of charge of three cask washings is 60 ℃; Deliver to three again and wash the thickening of stiff device; And through three wash the whizzer solid-liquid separation after, obtain three grades of solid ammonium chlorides and deliver to kiln dried, obtain electronic-grade ammonium chloride finished product after the packing; Three wash stiff device overflowing liquid and three washes separating machine filtrating and returns three cask washings and recycle, and after alkalimetal ion concentration such as the sodium in three cask washings, potassium increased, part circulating mother liquor II was delivered in two cask washings, simultaneously the deionized water of supplemental heat in three cask washings; Behind third stage circulation cleaning, its ammonium chloride master content further is increased to 99.5-99.8%, and alkalimetal ion such as sodium, potassium and sulfate ion content all be reduced to below the 50ppm, reaches the quality index of electronic-grade ammonium chloride.
In the implementation process of the present invention; Relevant static equipment inside serves as a contrast and moulds processing in the requirement electronic-grade Production of Ammonium Chloride device; The titanium material that the flow passage components of relevant moving equipment adopt; And be equipped with the special facilities that removes, thus the polyvalent metal ion concentration such as iron in the product are dropped to below the 2ppm, reach the quality standard of electronic-grade ammonium chloride product.Require to join alkali and produce and supporting the brine refining device is arranged, thereby alkaline earth metal ion concentration such as calcium in the product, magnesium are dropped to below the 5ppm, reach the quality standard of electronic-grade ammonium chloride product; Require to join alkali and produce the best supporting sal prunella combination preparing device that has, remove the production load of foreign ions such as sulfate radical to reduce electronic-grade Production of Ammonium Chloride device.
Listed German E.Merck and product index of the present invention in the table 1, this shows, the electronic-grade ammonium chloride product that the present invention produces is suitable with German E.Merck standard quality.
Table 1 electronic-grade ammonium chloride quality standard
Principle of work of the present invention is: the present invention is a main raw material with the wet agriculture ammonium chloride that joins in the alkali production, with the deionized water equal solvent of ammonia mother liquor I and heat, through the washing of three stage countercurrents, produces qualified electronic-grade ammonium chloride product.It relies on the smart ammonium production technique of integrated process, washes the isolating wet smart ammonium of whizzer with the deionized water of heat to two and carries out third stage washing, and through operations such as stiff, spinning, drying and packings, produce electronic-grade ammonium chloride; Mother liquor after three grades of washings separate all returns couplet alkali production system and reuses.
Claims (3)
1. method of producing electronic-grade ammonium chloride, it is a raw material with agriculture ammonium chloride, carries out the washing of three stage countercurrents with cold ammonia mother liquor I and hot deionized water equal solvent, and then produces electronic-grade ammonium chloride, it comprises the steps:
(1) adopt the agriculture ammonium chloride that joins in the alkali production to mix agitator treating with ammonia mother liquor I; The solid-liquid volume ratio is 20-40% in mixing solutions during washing; Deliver to one again and wash the thickening of stiff device, and obtain one-level solid ammonium chloride and filtrating after washing the whizzer solid-liquid separation through one;
(2) said one-level solid ammonium chloride is delivered in two cask washings, carries out abundant agitator treating with the circulating mother liquor I as solvent, adds BaCl in the said circulating mother liquor I
2To remove SO
4 2-Deliver to two again and wash the thickening of stiff device; And obtaining secondary solid ammonium chloride and circulating mother liquor I after washing the whizzer solid-liquid separation through two, said circulating mother liquor I is back to carries out circulation cleaning in two cask washings;
(3) said secondary solid ammonium chloride is delivered in three cask washings; By deionized water and the abundant agitator treating of secondary solid ammonium chloride as the heat of solvent; Deliver to three again and wash the thickening of stiff device, and obtain three grades of solid ammonium chlorides and circulating mother liquor II after washing the whizzer solid-liquid separation through three, said circulating mother liquor II is back to carries out circulation cleaning in three cask washings; Said three grades of solid ammonium chlorides are delivered to drying oven and are carried out drying, obtain electronic-grade ammonium chloride finished product after the packing.
2. the method for production electronic-grade ammonium chloride according to claim 1 is characterized in that: adopt the agriculture ammonium chloride that joins in the alkali production to be wet agricultural ammonium in the said step (1); The solid-liquid volume ratio is 20-40% in mixing solutions when one-level solid ammonium chloride and circulating mother liquor I are washed in the said step (2); The solid-liquid volume ratio is 20-40% in mixing solutions when secondary solid ammonium chloride and hot deionized water wash in the said step (3); Solution temperature when washing in the said step (3) is 50-60 ℃.
3. the method for production electronic-grade ammonium chloride according to claim 1 and 2 is characterized in that: filtrating is back to and joins the alkali production system in the said step (1); Add BaCl in the said step (2)
2To remove SO
4 2-The permanent white mud that reaction generates, the liquid that behind press filtration, obtains are back to and join the alkali production system.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012103041131A CN102826570A (en) | 2012-08-24 | 2012-08-24 | Method for producing electronic-grade ammonium chloride |
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|---|---|---|---|
| CN2012103041131A CN102826570A (en) | 2012-08-24 | 2012-08-24 | Method for producing electronic-grade ammonium chloride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437097A (en) * | 2014-11-12 | 2015-03-25 | 天津渤化永利化工股份有限公司 | Back washing method for ceramic micro-filtration membrane for low-temperature purification combined-soda process mother liquid II |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544329A (en) * | 2003-11-11 | 2004-11-10 | 天津渤海化工有限责任公司天津碱厂 | Industrial ammonium chloride production method from agricultural ammonium chloride in cool crystallizer |
| CN102234120A (en) * | 2011-03-29 | 2011-11-09 | 湖北双环科技股份有限公司 | Method for producing high-class purified ammonium by washing ammonium chloride with ammonia liquor |
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2012
- 2012-08-24 CN CN2012103041131A patent/CN102826570A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544329A (en) * | 2003-11-11 | 2004-11-10 | 天津渤海化工有限责任公司天津碱厂 | Industrial ammonium chloride production method from agricultural ammonium chloride in cool crystallizer |
| CN102234120A (en) * | 2011-03-29 | 2011-11-09 | 湖北双环科技股份有限公司 | Method for producing high-class purified ammonium by washing ammonium chloride with ammonia liquor |
Non-Patent Citations (2)
| Title |
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| 周俊华: "氨母液洗涤法生产精铵", 《纯碱工业》 * |
| 杨祥发等: "热水洗涤法生产低钾钠氯化铵工艺研究", 《无机盐工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437097A (en) * | 2014-11-12 | 2015-03-25 | 天津渤化永利化工股份有限公司 | Back washing method for ceramic micro-filtration membrane for low-temperature purification combined-soda process mother liquid II |
| CN104437097B (en) * | 2014-11-12 | 2016-05-04 | 天津渤化永利化工股份有限公司 | The back-washing method of the female II liquid of low temperature purification connection alkali ceramic micro filter film used |
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Application publication date: 20121219 |