CN102145901B - Method for recovering ammonium chloride by preparing complex salt of magnesium ammonium chloride hexahydrate - Google Patents
Method for recovering ammonium chloride by preparing complex salt of magnesium ammonium chloride hexahydrate Download PDFInfo
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- CN102145901B CN102145901B CN 201010108996 CN201010108996A CN102145901B CN 102145901 B CN102145901 B CN 102145901B CN 201010108996 CN201010108996 CN 201010108996 CN 201010108996 A CN201010108996 A CN 201010108996A CN 102145901 B CN102145901 B CN 102145901B
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Abstract
The invention relates to a method for recovering ammonium chloride by preparing complex salt of magnesium ammonium chloride hexahydrate (HH4MgC13 6H2O). The method comprises the following steps of: placing aqueous solution of ammonium chloride into a crystallizing kettle; regulating the pH of the solution to 4 to 6 by hydrochloric acid; controlling the temperature of the crystallizing kettle in the range of 10 to 80 DEG C; adding magnesium chloride into the crystallizing kettle under the stirring condition, stopping adding the magnesium chloride when the concentration of the magnesium chloride in the solution reaches 3 to 5mol/L and then continuously stirring for 30 to 120 minutes; drying filtered solid to obtain magnesium ammonium chloride hexahydrate; and decomposing the magnesium ammonium chloride hexahydrate at a lower temperature of 0 to 50 DEG C to obtain solid of ammonium chloride. With the adoption of the method, no waste liquid is discharged in the whole process, and an ammonium chloride recovery process and a magnesium precipitating process are well integrated. The method has strong operability and is easy to realize industrialization.
Description
Technical field
The present invention relates to the preparation method of ammonium chloride, be particularly related to a kind of aqueous ammonium chloride solution and magnesium chloride (magnesium chloride bittern, hydrated magnesium chloride or Magnesium Chloride Anhydrous) of ammonium carbonate method or the heavy magnesium process by-product of ammonia process of using and be raw material, by crystalline six hydration magnesium ammonium chloride double salt, and double salt is decomposed obtain ammonium chloride and for sinking the method for the rich magnesium aqueous solution of magnesium at low temperatures.
Background technology
China's bittern magnesium resource is abundant, and a large amount of magnesium mainly is to be present in seawater, salt lake saline and the well halogen with muriatic form.Bittern obtains being rich in magnesium chloride saturated aqueous solution or magnesium chloride hydrate after carrying sodium, potassium.In addition, in titanium sponge was produced, the magnesium metal reduction titanium tetrachloride was adopted in the production of titanium sponge more, produced a large amount of Magnesium Chloride Anhydrouss in the production process.At present, existing many bibliographical informations use the magnesium resource of these high-qualitys for the production of meticulous magnesium products of high added value such as magnesiumcarbonate hydrate, magnesium hydroxide and magnesium oxide.These technology have not only solved the problem of complex utilization of China's magnesium resource, and provide important support for the strategy of sustainable development of china natural resources.In these technology, mostly relate to ammonium carbonate method or ammonia process precipitation magnesium, and after the magnesium precipitate thing that will obtain separates, all can obtain being rich in the aqueous solution of ammonium chloride, its ammonium chloride concentration is 1～6mol/L.For example, prepare magnesium hydroxide with ammonia precipitation magnesium, separate the filtrate that will obtain being rich in ammonium chloride behind the magnesium hydroxide solid; When preparing the magnesiumcarbonate hydrate with ammonia and carbonic acid gas or ammonium bicarbonate precipitation magnesium, separate the filtrate that obtains equally being rich in ammonium chloride behind the magnesiumcarbonate hydrate.Ammonium chloride all is widely used in all conglomeraties such as chemical fertilizer, rubber, leather, pigment, takes appropriate means that ammonium chloride is reclaimed and not only has great economy value, and the development and use of China's magnesium resource are had great importance.
At present the recovery technology of ammonium chloride mainly is divided into two classes.The one, the employed unslaked lime ammonia still process of Sol dimension alkaline method method, this method reclaims the form of ammonium chloride with ammonia, but the calcining of necessary Wingdale and slaked lime ammonia still process all are the high energy consumption processes in the process, and by-product calcium chloride.The 2nd, the method for utilizing sodium-chlor to saltout to obtain ammonium chloride of using in the Hou's process for soda production, the application that this method is succeeded in alkali producing process, but salting-out agent are sodium-chlor, thereby can't directly be generalized to other chemical process.
Summary of the invention
The objective of the invention is to overcome the prior art weak point, for the problem of recovery ammonium chloride in the aqueous ammonium chloride solution that solves by-product in the meticulous magnesium products production process, and for save energy, reduce cost and increase economic benefit; Thereby provide a kind of aqueous ammonium chloride solution take the heavy magnesium process by-product of ammonium carbonate method or ammonia process and magnesium chloride (magnesium chloride bittern, hydrated magnesium chloride or Magnesium Chloride Anhydrous) to prepare six hydration magnesium ammonium chlorides as raw material, and the six hydration magnesium ammonium chlorides that will obtain decompose the aqueous solution that obtains ammonium chloride and be rich in magnesium for the heavy magnesium of ammonium carbonate method or ammonia process at low temperatures, the method adopts the mode of Recycling Mother Solution, without discharging of waste liquid with reduced environmental pollution.
The method that reclaims ammonium chloride by preparation six hydration magnesium ammonium chloride double salt of the present invention, to prepare six hydration magnesium ammonium chlorides take the aqueous ammonium chloride solution of the heavy magnesium process by-product of ammonium carbonate method or ammonia process and magnesium chloride (magnesium chloride bittern, hydrated magnesium chloride or Magnesium Chloride Anhydrous) as raw material, and the six hydration magnesium ammonium chlorides that will obtain decompose the method that obtains ammonium chloride under low temperature, and technique comprises the crystallization of six hydration magnesium ammonium chlorides and the low-temperature decomposition operation of six hydration magnesium ammonium chlorides; May further comprise the steps:
(1) preparation six hydration magnesium ammonium chlorides
Ammonium carbonate method or the heavy magnesium process side product sodium chloride aqueous solution of ammonia process are placed crystallization kettle, adjust pH value of solution to 4～6 with hydrochloric acid (HCl content is greater than 5wt%), crystallization control still temperature is 10～80 ℃, under agitation condition, in crystallization kettle, add again magnesium chloride, when the Chlorine in Solution magnesium density reaches 3～5mol/L, stop to feed in raw material, continue to stir 30～120 minutes; Solid drying after the filtration obtains six hydration magnesium ammonium chlorides.The filtrate that obtains after the filtration then is used as the raw material of heavy magnesium process;
(2) six hydration magnesium ammonium chloride recovery ammonium chlorides
Step (1) six hydration magnesium ammonium chloride is placed reactor, then the aqueous ammonium chloride solution that adds the heavy magnesium process by-product of tap water or ammonium carbonate method or ammonia process, the mass ratio that adds tap water or the side product sodium chloride aqueous solution and six hydration magnesium ammonium chlorides is 0.7: 1～1.8: 1; Then add the concentration of magnesium chloride magnesium chloride in the conditioned reaction still in the reactor as 1～3mol/L, temperature of reaction kettle is controlled to be 0～50 ℃, and decomposition reaction was carried out 10～150 minutes, and the solid drying after the filtration obtains ammonium chloride product, its purity＞95%.
In technique scheme, the aqueous ammonium chloride solution that the filtrate that obtains after filtering in the step (2) is then returned step (1) and heavy magnesium process by-product mixes as the raw material for preparing six hydration magnesium ammonium chlorides.
In technique scheme, the aqueous ammonium chloride solution that uses in step (1) and the step (2) is from the filtrate of ammonium carbonate method or the heavy magnesium process of ammonia process, and ammonium chloride concentration is 1～6mol/L.
In technique scheme, the magnesium chloride that uses in step (1) and the step (2) is magnesium chloride bittern, hydrated magnesium chloride or Magnesium Chloride Anhydrous.
Technical scheme of the present invention is that the aqueous ammonium chloride solution crystallization in the situation that adds magnesium chloride with the heavy magnesium by-product of ammonium carbonate method or ammonia process obtains six hydration magnesium ammonium chlorides, makes the solid decomposition obtain ammonium chloride thereby at low temperatures six hydration magnesium ammonium chlorides and the aqueous ammonium chloride solution of water or by-product are mixed by a certain percentage.Reaction principle is as follows:
NH
4Cl+MgCl
2+6H
2O＝NH
4MgCl
3·6H
2O↓
NH
4MgCl
3·6H
2O＝NH
4Cl↓+MgCl
2+6H
2O
Symbol: ↓--crystallization
Technical scheme of the present invention utilizes the crystallization in solution of ammonium chloride and magnesium chloride to generate six hydration magnesium ammonium chloride double salt, thereby and under cold condition, six hydration magnesium ammonium chlorides are added water decomposition and obtain chloride solid ammonium chloride is reclaimed, process can be finished by transition temperature under cold condition.The solution that is rich in magnesium chloride that process obtains is as the stock liquid of heavy magnesium.So not only be conducive to integrate Production Flow Chart, can reduce meticulous magnesium products production process to the impact of environment simultaneously, and produce obvious economic benefit.Method provided by the invention is easy, and is workable, is easy to realize industrialization.
Advantage of the present invention and active effect are:
(1) utilize magnesium chloride (magnesium chloride bittern, hydrated magnesium chloride or Magnesium Chloride Anhydrous) to reclaim ammonium chloride in the precipitation magnesium process efflux wastewater, the ammonium chloride that has effectively solved by-product in the meticulous magnesium products production process reclaims problem.The solution that is rich in magnesium chloride that obtains has realized that as the raw material of heavy magnesium process ammonium chloride reclaims the flow process of producing with meticulous magnesium products and integrates.Thereby solved the higher value application problem of a large amount of by-product Magnesium Chloride Anhydrouss that produce in present seawater or salt lake brine magnesium resource and the titanium sponge production process, promoted industrial chain value and improved ecotope.
(2) prepared purity of ammonia chloride more than 95%, can directly be used as chemical fertilizer, also can behind recrystallization, obtain highly purified ammonium chloride product and supply with other meticulous industries.
(3) method that reclaims ammonium chloride through preparing six hydration magnesium ammonium chloride low-temperature decomposition that adopts, the steam output that reclaims the ammonium chloride process need is little, and energy consumption is low.The fertile purity of the ammonium that obtains is high, and added value is high, has good economic benefit.
(4) the Recycling Mother Solution mode that adopts has been saved water of productive use greatly.Process effluxes without waste water, to environment without negative impact.
Description of drawings
Fig. 1. process flow diagram of the present invention.
Fig. 2 a is the SEM figure of the six hydration magnesium ammonium chlorides that obtain of embodiment 1;
Fig. 2 b is the SEM figure that embodiment 1 obtains corresponding ammonium chloride product;
Fig. 2 c is the XRD figure spectrum that embodiment 1 obtains six hydration magnesium ammonium chlorides and corresponding ammonium chloride product.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done in further detail explanation
Embodiment 1
The concrete technology flow process of present embodiment sees also Fig. 1.
The raw material ammonium chloride solution that present embodiment is selected is the byproduct in the heavy magnesium process, the byproduct of described heavy magnesium process, and for example by the ammonium chloride solution in ammonium carbonate method or the heavy magnesium process of ammonia process, the concentration of ammonium chloride solution is 6mol/L; Ammonium chloride solution 400ml is added crystallization kettle, adjusts the interior ammonium chloride solution pH=4 of this crystallization kettle with hydrochloric acid (15wt%), add Saturated with Magnesium chloride bittern again until in the crystallization kettle density of magnesium chloride reach 3mol/L; Be under 10 ℃ of conditions in crystallization control still temperature, continue to stir 120 minutes; Obtain the solid drying after the filtration and obtain six hydration magnesium ammonium chloride 109g.It is 0.7: 1 ratio according to the mass ratio of tap water and six hydration magnesium ammonium chlorides, the 109g six hydration magnesium ammonium chlorides adding that obtains is filled in the reactor of 76g tap water, add again Saturated with Magnesium chloride bittern 20ml, density of magnesium chloride is 3mol/L in the reactor, temperature of reaction kettle is 0 ℃, and decomposition reaction was carried out 150 minutes.The solid drying that obtains after the suspension filtered in the reactor is obtained 10g ammonium chloride, and its purity is 96%.Fig. 2 a is the SEM figure of the six hydration magnesium ammonium chlorides that obtain of embodiment 1; Fig. 2 b is the SEM figure that embodiment 1 obtains corresponding ammonium chloride product; Fig. 2 c is the XRD figure spectrum that embodiment 1 obtains six hydration magnesium ammonium chlorides and corresponding ammonium chloride product.
Embodiment 2
The concrete technology flow process of present embodiment sees also Fig. 1.
Heavy magnesium side product sodium chloride solution 800ml in ammonium carbonate method or the heavy magnesium process of ammonia process is added crystallization kettle, wherein, this ammonium chloride solution concentration is 1mol/L, adjust this ammonium chloride solution pH=6 with hydrochloric acid (5wt%), add Magnesium Chloride Anhydrous again until in the crystallization kettle density of magnesium chloride reach 5mol/L; Be under 80 ℃ of conditions in crystallization control still temperature, continue to stir 30 minutes; Solid drying after the filtration obtains six hydration magnesium ammonium chloride 395g.Be that 1.8: 1 ratio adds the 395g six hydration magnesium ammonium chlorides that obtain and fills 711g to sink magnesium by-product concentration be in the reactor of aqueous ammonium chloride solution of 1mol/L according to the mass ratio of the ammonium chloride solution of heavy magnesium by-product and six hydration magnesium ammonium chlorides, add again Magnesium Chloride Anhydrous 50.8g, density of magnesium chloride is 2.3mol/L in the reactor, temperature of reaction kettle is 50 ℃, and decomposition reaction was carried out 10 minutes.The solid drying that obtains after the suspension filtered in the reactor is obtained 157g ammonium chloride, and its purity is 98%.
Embodiment 3
The concrete technology flow process of present embodiment sees also Fig. 1.
With the heavy magnesium side product sodium chloride solution 400ml of ammonium carbonate method or ammonia process in embodiment 2 behind the six hydration magnesium ammonium chloride recovery ammonium chlorides resulting filtered liquid 200ml add crystallization kettle, wherein, this ammonium chloride solution concentration is 3mol/L, again ammonium chloride solution is adjusted ammonium chloride solution pH=4.5 with hydrochloric acid (36wt%), add magnesium chloride hexahydrate again until in the crystallization kettle density of magnesium chloride reach 3.5mol/L; Be under 40 ℃ of conditions in crystallization control still temperature, continue to stir 100 minutes; The solid drying that obtains after the filtration obtains six hydration magnesium ammonium chloride 256g.Be that 1.37: 1 ratio adds 256g six water that obtain and magnesium ammonium chloride and fills 350g to sink magnesium by-product concentration be in the reactor of aqueous ammonium chloride solution of 3mol/L according to the mass ratio of the ammonium chloride solution of heavy magnesium by-product and six hydration magnesium ammonium chlorides, add Magnesium dichloride hexahydrate 95g, density of magnesium chloride is 1mol/L in the reactor again.Temperature of reaction kettle is 5 ℃, and decomposition reaction was carried out 150 minutes.Suspension filtered in the reactor or the solid drying that obtains are obtained 85g ammonium chloride, and its purity is 98%.
Claims (5)
1. the method by preparation six hydration magnesium ammonium chloride double salt recovery ammonium chloride is characterized in that, may further comprise the steps:
1) preparation six hydration magnesium ammonium chlorides: aqueous ammonium chloride solution is placed crystallization kettle, with content greater than the hydrochloride adjusted solution pH to 4 of 5wt% ~ 6, crystallization control still temperature is 10 ~ 80 ℃, under agitation condition, in crystallization kettle, add magnesium chloride, when the Chlorine in Solution magnesium density reaches 3 ~ 5mol/L, stop to feed in raw material, continue to stir 30 ~ 120 minutes; Solid after the filtration obtains six hydration magnesium ammonium chlorides through super-dry;
2) six hydration magnesium ammonium chloride recovery ammonium chlorides: the six hydration magnesium ammonium chlorides that step 1) is obtained place reactor, then add tap water or aqueous ammonium chloride solution, the mass ratio of the tap water that wherein, adds or aqueous ammonium chloride solution and six hydration magnesium ammonium chlorides is 0.7:1 ~ 1.8:1; And then the concentration that adds magnesium chloride magnesium chloride in the conditioned reaction still in the reactor is as 1 ~ 3mol/L, and temperature of reaction kettle is controlled at 0 ~ 50 ℃ and carries out decomposition reaction, and the decomposition reaction time is 10 ~ 150 minutes; Solid drying after the filtration obtains the finished product ammonium chloride.
2. according to claim 1ly reclaiming the method for ammonium chloride by preparation six hydration magnesium ammonium chloride double salt, it is characterized in that, is the aqueous ammonium chloride solution of the by-product that obtains of the heavy magnesium process of ammonium carbonate method or ammonia process at the aqueous ammonium chloride solution described in the step 1).
3. the method by preparation six hydration magnesium ammonium chloride double salt recovery ammonium chloride according to claim 1 is characterized in that ammonium chloride concentration is 1 ~ 6mol/L in the described aqueous ammonium chloride solution.
4. the method by preparation six hydration magnesium ammonium chloride double salt recovery ammonium chloride according to claim 1 is characterized in that, filters the then magnesium chloride of the heavy magnesium process of conduct of gained filtrate in step 1); Step 2) filtering gained filtrate in returns step 1) and mixes with the aqueous ammonium chloride solution of heavy magnesium process by-product and be used as the raw material for preparing six hydration magnesium ammonium chlorides.
5. according to claim 1ly reclaim the method for ammonium chloride by preparation six hydration magnesium ammonium chloride double salt, it is characterized in that, in step 1) and step 2) described in magnesium chloride be magnesium chloride bittern, hydrated magnesium chloride or Magnesium Chloride Anhydrous.
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| CN107098372A (en) * | 2017-04-19 | 2017-08-29 | 湖北三宁化工股份有限公司 | A kind of method that hydrochloric acid decomposes phosphorus mine tailing extracting sulfuric acid calcium pyroborate and magnesium hydroxide |
| CN110606610B (en) * | 2019-08-30 | 2022-05-17 | 河南佰利联新材料有限公司 | Method for circularly treating metal chloride waste liquid by ammonia process |
| CN113106497B (en) * | 2021-04-09 | 2022-04-01 | 河北大有镁业有限责任公司 | Method for continuously producing raw materials for electrolytic rare earth magnesium alloy by utilizing hydrolysis-chlorination coupling reaction |
| CN113184880A (en) * | 2021-04-21 | 2021-07-30 | 武汉工程大学 | Method for separating ammonium chloride and potassium chloride mixture based on three-stage crystallization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5439563A (en) * | 1993-08-25 | 1995-08-08 | Alcan International Limited | Electrolytic production of magnesium metal with feed containing magnesium chloride ammoniates |
| CN1689973A (en) * | 2004-04-29 | 2005-11-02 | 中南大学 | Preparation method of high-purity anhydrous magnesium chloride |
| CN101259968A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院过程工程研究所 | Method for preparing trihydrated magnesium carbonate from magnesium chloride-containing bittern by using ammonium carbonate |
| CN101323457A (en) * | 2008-07-25 | 2008-12-17 | 国家海洋局天津海水淡化与综合利用研究所 | Method for preparing potassium muriate by using sea water |
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2010
- 2010-02-08 CN CN 201010108996 patent/CN102145901B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5439563A (en) * | 1993-08-25 | 1995-08-08 | Alcan International Limited | Electrolytic production of magnesium metal with feed containing magnesium chloride ammoniates |
| CN1689973A (en) * | 2004-04-29 | 2005-11-02 | 中南大学 | Preparation method of high-purity anhydrous magnesium chloride |
| CN101259968A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院过程工程研究所 | Method for preparing trihydrated magnesium carbonate from magnesium chloride-containing bittern by using ammonium carbonate |
| CN101323457A (en) * | 2008-07-25 | 2008-12-17 | 国家海洋局天津海水淡化与综合利用研究所 | Method for preparing potassium muriate by using sea water |
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