CN1013768B - Process for treatment waste solution containing ammonium ions and fluorineions - Google Patents
Process for treatment waste solution containing ammonium ions and fluorineionsInfo
- Publication number
- CN1013768B CN1013768B CN 85101146 CN85101146A CN1013768B CN 1013768 B CN1013768 B CN 1013768B CN 85101146 CN85101146 CN 85101146 CN 85101146 A CN85101146 A CN 85101146A CN 1013768 B CN1013768 B CN 1013768B
- Authority
- CN
- China
- Prior art keywords
- ion
- exchange resin
- ammonium
- ion exchange
- waste liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The present invention relates to an operating process for treating waste liquid with ammonium ions and fluorine ions to recover ammonia water and anhydrous hydrogen fluoride. Strong acid type ion exchange resin is used for treating the waste liquid to separate the ammonium ions; hydrochloric acid is used for rinsing the strong acid type ion exchange resin, and ammonia is recovered in the form of ammonium chloride; concentrated sulfuric acid is added and discharge liquid is distilled to recover the hydrogen fluoride; the rest diluted sulfuric acid is concentrated and is repeated to be used for process steps of recovering the hydrogen fluoride; magnesium hydroxide is added to ammonium chloride solution to carry out distillation to recover ammonia water; the rest magnesium chloride is carried out for thermal decomposition into hydrochloric acid and magnesium hydroxide which are respectively repeatedly used for treating regeneration of ion-exchange resin, and the ammonium chloride solution.
Description
The present invention relates generally to the technological process of a kind of processing from the waste liquid that contains ammonium ion and fluorion in the uranium nuclear fuel production, comprising the recovery and the recycling of anhydrous hydrogen fluoride (hydrofluoric acid) and ammonia.
Uranium dioxide is a kind of typical nuclear fuel material, and it is to be generated by the uranium hexafluoride of uranium nuclear fuel factory.In the technology that generates intermediate product two ammonium uranates, produce a kind of waste liquid that contains ammonium ion and fluorion.At present, the processing of this waste liquid is to make waste liquid be separated into ammoniacal liquor and Calcium Fluoride (Fluorspan) with calcium hydroxide in uranium nuclear fuel factory, and has only ammoniacal liquor can be repeated to utilize in the production of nuclear fuel material.
Calcium Fluoride (Fluorspan) is in nuclear fuel factory, because it can't directly utilize at factory, so just simply with it storage with stacking.Outside nuclear fuel factory, Calcium Fluoride (Fluorspan) can be used as the initial feed of producing anhydrous hydrofluoric acid.But in this case,, just need additional art breading in order in nuclear fuel factory, to provide this material as gratifying raw material.This system is complicated therefrom.Produce hydrofluoric acid from Calcium Fluoride (Fluorspan), also generate the by product that can't directly utilize simultaneously.
The present invention is directed to the waste liquid that contains Neutral ammonium fluoride and ammoniacal liquor of handling uranium nuclear fuel factory, reclaim fluorine material and ammonia material respectively and drop to minimum level with the waste material that will produce, wherein, the fluorine material can reclaim with the form of anhydrous hydrogen fluoride, and it is to be used for the raw material that uranium hexafluoride changes.In addition, in technology of the present invention, be used for reagent energy cycling and reutilization after handling of above-mentioned sepn process, thereby make the amount of waste material drop to bottom line.Because the characteristic of magnesium chloride, we utilize the related characteristics of magnesium chloride to design the combined production process that achieves the above object, thereby have finished the present invention.
The invention provides a kind of closed cycle system and handle the method for the waste liquid that contains ammonium ion and fluorion, it comprises with strong acid ion exchange resin carries out ion-exchange absorption effect to ammonium ion and makes it separation; If desired, distill concentrated to the hydrogen fluoride dilute solution that stays; Add the vitriol oil and reclaim hydrogen fluoride with the extractive distillation method; Concentrate remaining dilute sulphuric acid, circulate it to aforesaid extractive distillation workshop section; Adsorbed the ion exchange resin of ammonium ion with hydrochloric acid soln regeneration, the resin of removing ammonium ion has been used for adsorbing ammonium ion once more; From the aqueous ammonium chloride solution of remainder, add magnesium hydroxide, through distilling to reclaim ammoniacal liquor; Contain magnesium chloride in the rest solution, water is separated thermal decomposition method and is reclaimed hydrochloric acid and magnesium hydroxide; Hydrochloric acid is recycled to the regeneration of ion-exchange resin operation, and this magnesium hydroxide is recycled to from the operation of ammonium chloride solution distillation ammoniacal liquor.
Method of the present invention can not only be applied to handle the waste liquid of uranium nuclear fuel factory, and can be used for handling any NH of containing usually
+ 4And F
-Waste liquid.In this case, the foreign ion of other a small amount of coexistence can't give rise to trouble.But the content as them is very big, can be removed with appropriate means in advance.
Usually, waste liquid at first through ion-exchange absorption effect to separate ammonium ion.In this procedure, use strongly acidic cation-exchange.The Zeo-karb of any resin carrier, as polystyrene type, the phenol type, graphite moulds etc. as long as they have strong acid group, just all can be used.Use these ion exchange resin both can make pending waste liquid, also can simply resin be mixed with pending waste liquid, stir, and then give separation by the resin packed column.The consumption of the resin of filling or mixing use can be according to NH in the pending waste liquid like this
+ 4And F
-Concentration and suitably change.When using strong acid ion exchange resin, can consider the acidity of pending waste liquid, therefore, employed waste liquid, the acidity that just need not regulate it.
Change the waste liquid of factory again about uranium hexafluoride, after ion exchange treatment, its water is actually a kind of solution that only contains percentum HF.Add the vitriol oil (70% or higher) to waste liquid, distilled with known method, it is nearly 90% from then on to reclaim total fluorine content with the form of anhydrous hydrogen fluoride in the waste liquid, and in fact better method is earlier by distilling, and makes HF content bring up to about 30%.Sulfur waste acid in this procedure can change into the vitriol oil in next step distillation concentrates one by one, and can use in the extractive distillation operation.Therefore the moisture that in the HF enrichment process, steams and collect, and steam in the sulphuric acid concentration operation that only do will be by the waste material of tipping with collected moisture.Only contain a spot of impurity such as HF in this waste water, thereby the method for available routine is handled it.The solid waste that discards in the technology of the present invention is a minute quantity.
On the other hand, contain NH because of absorption
+ 4Ion exchange resin promptly separated NH through regeneration
+ 4Can utilize again afterwards.Any mineral acid all can be used to desorb.But under condition of the present invention, must use hydrochloric acid, because be intended to reclaim ammonia.From the aqueous ammonium chloride solution that gets like this, also boil simply with regard to recyclable ammoniacal liquor as long as add magnesium hydroxide.Per 1 mole of ammonium chloride adds 0.5 mole magnesium hydroxide at least.In this procedure, concentration is that 3～20% ammoniacal liquor can obtain 97% recovery approximately, and what stay is magnesium chloride brine.
This kind magnesium chloride brine is heated decomposition in next procedure, and hydrochloric acid was steamed and stayed the slurry of magnesium hydroxide this moment.These materials can be used further in the operation of front, and can reuse, until except NH
+ 4Positively charged ion in addition is accumulated in the magnesium hydroxide, makes it to continue till the recirculation.
The gained conclusion is, in the technology by the present invention's proposition, having only the water that contains the small amount of fluorine material that produces in the sulphuric acid concentration operation is unique waste material, ammoniacal liquor and anhydrous hydrogen fluoride all are recovered in the mode of directly utilizing again, and the whole materials that participate in this technology are all repeatedly used in the closed system of this technology.
Now, this technology is described with reference to the accompanying drawings one by one.
Unique accompanying drawing is the particular flow sheet of technological process of the present invention.
Said in the following description per-cent is weight ratio.
Get 10 liters and contain 5%NH
4F and 2%NH
4The simulated waste of OH allows it by having filled 2 liters of strong acid ion exchange resins (ion exchange resin 120, Luo Meng and Haas (Amberlite IR120, Rohm; Hass)) pillar.Ammonium ion is attracted on the ion exchange resin, and concentration is about 2.7% HF aqueous solution outflow pillar.With 6 premium on currency eluent ion exchange resins, effluent liquid and above-mentioned effluent liquid merge.Obtain HF concentration like this and be about 1.5% solution.
This HF solution distills in distillation column, emits the aqueous solution of the about 32%HF of concentration from the bottom, and water (vapour) is emitted from the top.The HF solution that to emit from the column bottom changes the extractive distillation post over to, adds 1.8 liters of 80%H in post from the top
2SO
4, beginning extractive distillation.Top from post can obtain 2.5 liters of anhydrous hydrofluoric acids like this.Emit concentration from the bottom and be about 68% sulfur waste acid.This sulfur waste acid transpiring moisture and be concentrated into 80% concentration in evaporating column, and be recycled and be used for the extractive distillation post.The HF that is not reclaimed by the form with anhydrous hydrogen fluoride in the extractive distillation post is about 1% of total amount, and these solution are emitted with moisture evaporated in the sulphuric acid concentration post.
Be adsorbed on the ammonium ion on the ion exchange resin in the exchange operations technology, desorb by about 6 liters 3N HCl solution.Ion exchange resin after the ammonium ion desorb can be recycled and reused for ion-exchange process next time.That operation is discharged in regeneration and the washing is about 4% NH
4CL solution.Add about 0.6 kilogram Mg(OH to this solution)
2, the gained mixed solution is heated, and condensation discharges ammoniated steam, can obtain about 5 liters of concentration and be about 15% NH
4The OH aqueous solution.
Remaining concentration is about 5% MgCL
2The aqueous solution is divided into Mg(OH through the hydrolysis thermal degradation)
2With the HCL aqueous solution, every kind of material all can reuse in this technology.
Repeat the aforesaid operations process, 1 cubic metre of waste liquid of co-processing.Through current operation, not observe used ion exchange resin and deterioration occurs, loss is lower than 2%.The loss that other used material is sulfuric acid, hydrochloric acid and magnesium hydroxide is lower than 5%.The hydrofluoric acid that reclaims and the amount of ammoniacal liquor are respectively 21.6 liters and 510 liters, and the rate of recovery is respectively 97% and 93%.The amount that produces waste water is 2.43 cubic metres, and wherein fluorine content is 0.096 grams per liter.
Claims (2)
1, a kind of closed cycle system is handled the waste liquid that contains ammonium ion and fluorion, especially handles the method from the waste liquid of nuclear uranium fuel factory, it is characterized in that comprising with strong acid ion exchange resin and carries out ion-exchange absorption ammonium ion; In containing rare hydrofluoric effluent liquid, add the vitriol oil and carry out extractive distillation, reclaim hydrogen fluoride; Concentrate remaining dilute sulphuric acid, be recycled to above-mentioned extractive distillation operation; Adsorb the ion exchange resin of ammonium ion with aqueous solution of hydrochloric acid regeneration, utilized the described ion exchange resin of having removed ammonium ion to remove to adsorb ammonium ion once more again; Add magnesium hydroxide in the aqueous ammonium chloride solution of remainder, then ammoniacal liquor is reclaimed in distillation; Contain from remaining with hydrolysis thermal degradation method and reclaim hydrochloric acid and magnesium hydroxide the solution of magnesium chloride; The hydrochloric acid that reclaims recycles in the operation of ion exchange resin regeneration, and the magnesium hydroxide of recovery recycles the operation that distills out ammoniacal liquor from ammonium chloride solution.
2, method according to claim 1 is characterized in that wherein concentrating remaining rare hydrogen fluoride solution with distillation method carry out ion-exchange absorption ammonium ion with strong acid ion exchange resin after.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101146 CN1013768B (en) | 1985-04-01 | 1985-04-01 | Process for treatment waste solution containing ammonium ions and fluorineions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101146 CN1013768B (en) | 1985-04-01 | 1985-04-01 | Process for treatment waste solution containing ammonium ions and fluorineions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101146A CN85101146A (en) | 1987-01-17 |
| CN1013768B true CN1013768B (en) | 1991-09-04 |
Family
ID=4791652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101146 Expired CN1013768B (en) | 1985-04-01 | 1985-04-01 | Process for treatment waste solution containing ammonium ions and fluorineions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1013768B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008101137A1 (en) * | 2007-02-16 | 2008-08-21 | 3M Innovative Properties Company | System and process for the removal of fluorochemicals from water |
| CN101475194B (en) * | 2009-01-22 | 2010-12-29 | 西安西骏新材料有限公司 | Method for recycling ammonia from low concentration ammonium chloride wastewater |
| CN102659089B (en) * | 2012-04-25 | 2014-06-04 | 中国科学院过程工程研究所 | Producing method of calcium hydrogen phosphate |
| CN102816047B (en) * | 2012-08-07 | 2014-12-24 | 南通市振兴精细化工有限公司 | Technology for removing ammonia in ammoniacal smell ethanol in tetramethylpiperidinol |
| CN105803204A (en) * | 2014-12-31 | 2016-07-27 | 胡桂生 | Heavy metal-containing waste liquid purifying and impurity removing method and composite set thereof |
| CN105947984A (en) * | 2016-05-20 | 2016-09-21 | 同济大学 | Production process for recycling and producing anhydrous hydrogen fluoride from high-concentration wastewater containing fluoride |
| CN106241740B (en) * | 2016-08-31 | 2018-09-25 | 贵阳开磷化肥有限公司 | A method of producing anhydrous hydrogen fluoride from ammonium fluoride acidolysis mixed liquor |
| CN106977034B (en) * | 2017-03-16 | 2022-03-22 | 中国核电工程有限公司 | Method for recovering hydrogen fluoride from high-concentration fluorine-containing wastewater |
| CN109516631A (en) * | 2019-01-28 | 2019-03-26 | 湖南工业大学 | A kind of processing method of fluorine-containing ammonia nitrogen waste water |
| 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 |
| CN113369291B (en) * | 2020-03-09 | 2022-05-06 | 有研稀土新材料股份有限公司 | Method for repairing ionic rare earth ore ammonium salt leaching site |
| CN114149131B (en) * | 2021-12-18 | 2023-07-04 | 江苏电科环保有限公司 | Treatment method of fluorine-containing etching waste liquid for controlling COD concentration |
-
1985
- 1985-04-01 CN CN 85101146 patent/CN1013768B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85101146A (en) | 1987-01-17 |
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