CN104071941B - In a kind of recovering rare earth ammonium salt waste water, ammonium chloride prepares the method for agrochemical - Google Patents
In a kind of recovering rare earth ammonium salt waste water, ammonium chloride prepares the method for agrochemical Download PDFInfo
- Publication number
- CN104071941B CN104071941B CN201410287049.XA CN201410287049A CN104071941B CN 104071941 B CN104071941 B CN 104071941B CN 201410287049 A CN201410287049 A CN 201410287049A CN 104071941 B CN104071941 B CN 104071941B
- Authority
- CN
- China
- Prior art keywords
- waste water
- ammonium salt
- ammonium chloride
- waste
- concentration
- 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 - Fee Related
Links
Landscapes
- Fertilizers (AREA)
Abstract
In a kind of recovering rare earth ammonium salt waste water, ammonium chloride prepares the method for agrochemical, rare earth ammonium salt waste water is mainly first entered electrodialysis concentrating unit by it after Activated Carbon Pretreatment, waste water ammonium salt concentration is promoted to 10 ~ 13%, then 45 ~ 48% are concentrated into further through triple effect evaporation, by first for concentrated slurry crystallisation by cooling, then the required arbitrarily ratio being greater than 60% with the waste residue of other three kinds of activated process in ammonium salt mass concentration carries out compound, stir evenly rear rotary conveyor roller pelletizer of making a gift to someone and spray into the granulation of ammonium salt mother liquor, wherein other three kinds activation waste residues are gelatin factory phosphorus-containing waste slag activation products, power station straw ash activation products and weathered coal activation products.Processing costs of the present invention is low, non-secondary pollution, and fertilize preparation craft is simple, and fertilizer efficiency is good.
Description
Technical field
The invention belongs to wastewater treatment and resource recycling field, particularly a kind for the treatment of process of rare earth ammonium salt waste water.
Background technology
China's rare earth resources enriches, and the most rare earth elements needed for the current world are all separated with smelting in China's exploitation.But, in rare earth mining and smelting process, discharge various dissimilar high density pollution waste water, as acid waste water, fluoride waste, containing radioelement waste water, high-salt wastewater, high-concentration ammonia nitrogenous wastewater etc.In these dissimilar waste water, especially pollute the most outstanding with ammonia nitrogen waste water, its water yield is large, and ammonia nitrogen concentration is high.Ammonia nitrogen in rare earth metallurgy mainly exists with ammonium chloride form, and the ammonium chloride concentration of usual hight-concentration parts waste water is up to more than 100g/L, and middle its ammonium chloride concentration of Concentration portion waste water also can reach tens of g/L.If the ammonia nitrogen of high density like this is not treated or deal with improperly, great harm will be brought to environment, cause irremediable Ecological Loss, also will cause the waste of the useful resources such as ammonium chloride simultaneously, cause serious financial loss.Therefore, when carrying out rare earth metallurgy and administering, not only need the removal considering pollution substance, also need recovery and the utilization of carrying out valuable resource simultaneously.
Rare earth is in smelting sepn process, usually according to the ammonia nitrogen waste water of different process section discharge different concns, as the carbon ammonium precipitation waste water (ammonium chloride concentration is at about 40g/L) of the rare earth soap waste water (ammonium chloride concentration reaches 100g/L) of high-concentration ammonia-nitrogen, middle ammonia nitrogen concentration, low ammonia nitrogen concentration waste water (ammonium chloride concentration number g/L).At present, in such wastewater treatment, main according to different concns ammonia nitrogen waste water, different process is adopted to process respectively, ammonia nitrogen waste water for high density mainly adopts evaporation concentration method and electrodialysis-evaporation concentration combination process to process, and widely apply in this many rare earth ammonia nitrogens wastewater treatment at home and abroad, technology maturation is reliable, and can ammonium salt be reclaimed, substantially can offset equipment working cost; The intermediate concentration waste water that ammonia nitrogen concentration is relatively high, many employing ammonia aeration methods, this method treatment effect is better, invest relatively low, and recyclable ammoniacal liquor is back to production; Low Concentration Ammonia Containing Wastewater in Rare Earth Production waste water, because in waste water, organic content is few, biodegradability is poor, is difficult to adopt biochemical treatment, adopts additive method process such as absorption method, ion-exchange, breakpoint chlorination etc. to have part to report.
In sum, mainly there is following problem in the wastewater treatment of current rare earth ammonium salt and recycling:
1, different concns ammonia nitrogen waste water classification process, although effectively can remove ammonia nitrogen to reclaim valuable resource, but the waste water cost of centering, low ammonium salt concentration is higher, and economy is poor.
2, use evaporative crystallization method to reclaim ammonium salt, although can basic neutralisation processing costs, this be on the basis that can sell smoothly of the ammonium salt being based upon recovery.Because the ammonium chloride reclaimed can only be sold as agriculture fertilizer, and agriculture production is less to single ammonium chloride nitrogenous fertilizer demand, makes a large amount of ammonium salt reclaimed be difficult to effectively sell, and affects the process of ammonia nitrogen waste water.
Summary of the invention
The object of the invention is to solve above-mentioned the deficiencies in the prior art part, providing ammonium chloride in a kind of recovering rare earth ammonium salt waste water to prepare the method for agrochemical.The present invention mainly first adopts electrodialysis to concentrate to ammonium salt waste water, then enters triple effect evaporation crystal system and carry out concentrated thought, by while ammonium salt is effectively removed in waste water, adopts fertilize preparation craft, concentrated ammonium salt is prepared into agrochemical.
Technical scheme of the present invention is as follows:
1, the recovery of RE waste water ammonium chloride:
A, rare-earth smelting be separated the concentration of discharging be the ammonium salt waste water of 6 ~ 8% first through activated carbon column pre-treatment, make organic concentration in waste water reduce to below 0.5mg/L, then through security personnel filtration devices, to protect aftertreatment device;
B, above-mentioned waste water after pretreatment enter electrodialysis concentrating unit, and ammonium chloride concentration in waste water is promoted to 10 ~ 13%, then adopt HCl that pH in concentrated solution is adjusted to 3 ~ 5;
C, concentrated solution after electrodialysis concentrates enter triple-effect evaporator, and make ammonium chloride be concentrated into 45 ~ 48% further, gained ammonium chloride concentrated slurry enters fertilize preparation craft; Condensation distilled water returns production phase ammonium bicarbonate precipitation technological cycle and uses.
2, agrochemical is prepared:
A, ammonium salt concentrated solution crystallisation by cooling: step 1 is concentrated into slurries crystallisation by cooling in crystallisation by cooling groove of 45 ~ 48%, when temperature isolates crystallization chloride solid close to putting it into during normal temperature in separating centrifuge, a mother liquor part is used for the granulation of composite organic-inorganic fertilizer, and unnecessary mother liquor returns three-effect evaporation and condensation.
B, gelatin factory phosphorus-containing waste slag activation treatment: placed by gelatin factory phosphorus-containing waste slag, make its natural air drying, when moisture is less than 12%, adds vitriol oil adjustment pH and reach 4 ~ 5.5, place its natural reaction slaking of 1 ~ 3 angel.
C, power station straw ash activate: the straw ash in power station, in alkalescence, is neutralized pH with sulfuric acid and reaches 4.5 ~ 6.5, make the K in straw ash
2o is converted into K
2sO
4, medium trace element is converted into water soluble sulfate.
D, weathered coal activation treatment: bicarbonate of ammonia is added weathered coal and stirs, place 3 ~ 6 days, make pH reach 5 ~ 7, to improve the activity of Humic Acid from Weathered Coal.
E, the granulation of multielement compound organic and inorganic fertilizer: the ammonia chloride crystal that crystallization in the waste residue of three kinds of activated process in above-mentioned steps b, c, d and step a is gone out; the required arbitrarily ratio being greater than 60% in ammonium chloride mass concentration carries out compound; stir evenly rear rotary conveyor feeding roller pelletizer and spray into the granulation of ammonium salt mother liquor; roller drying machine is sent into after granulating; dry in dryer, finally by sieving, cool, the operation such as packaging makes product.
The present invention compared with prior art tool has the following advantages:
1, processing costs is low, effective.
2, local waste resource can be made full use of, realize turning waste into wealth.
3, the heavy metal in recovery ammonium chloride and other unfavorable elements can be made to be diluted, greatly can improve it and reach Agricultural Fertilizer standard, and there is not secondary pollution risk.
4, prepare composite fertilizer and greatly can improve fertilizer efficiency, overcome the simple ammonium chloride that uses as the shortcoming of chemical fertilizer, market outlet is good, realizes considerable enterprise profit.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that in the recovering rare earth ammonium salt waste water in the present invention, ammonium chloride prepares the method for agrochemical.
Embodiment
Embodiment 1
In a kind of recovering rare earth ammonium salt waste water, ammonium chloride prepares the method for agrochemical, as shown in Figure 1, first by the ammonium salt waste water of 8% through activated carbon column pre-treatment, organic concentration in waste water is made to reduce to 0.4mg/L, electrodialysis unit is entered after security personnel's filtration devices, ammonium chloride concentration in waste water is promoted to 12.5%, concentrated solution pH is adjusted to 4, enter the further concentration to 47% of triple effect evaporation crystallizer subsequently, then concentrated slurry enters crystallisation by cooling in crystallisation by cooling groove, when temperature reaches 27 DEG C, start separating centrifuge, reclaim chloride solid, the mother liquor of 60% is used for the granulation of composite organic-inorganic fertilizer, remain 40% mother liquor and return three-effect evaporation and condensation device.
Gelatin factory phosphorus-containing waste slag activation treatment: when being 11% by gelatin factory phosphorus-containing waste slag placement natural air drying to moisture, adds vitriol oil adjustment pH and reaches 5, then place its natural reaction slaking of 2 angels.
Power station straw ash activation: with sulfuric acid, the straw ash in power station being neutralized pH is 5, makes the K in straw ash
2o is converted into K
2sO
4, medium trace element is converted into water soluble sulfate.
Weathered coal activation treatment: bicarbonate of ammonia is added weathered coal and stirs, places 6 days, makes pH reach 6, improves the activity of Humic Acid from Weathered Coal.
By " three wastes " of the ammonium chloride of above-mentioned recovery and other three kinds of activated process according to ammonium chloride: phosphorus-containing waste slag slaking product: power station straw ash activation products: weathered coal activation products mass ratio equals 0.7:0.1:0.1:0.1 and carries out composite; mixing stirs evenly and sprays into the granulation of ammonium salt mother liquor with rotary conveyor roller pelletizer of making a gift to someone; roller drying machine is sent into after granulating; dry in dryer, finally by sieving, cool, the operation such as packaging is prepared into compound Agricultural Fertilizer.
Embodiment 2
By the ammonium salt waste water of 6% first through activated carbon column pre-treatment, organic concentration in waste water is made to reduce to 0.5mg/L, electrodialysis unit is entered after security personnel's filtration devices, ammonium chloride concentration in waste water is promoted to 11%, concentrated solution pH is adjusted to 4, enter the further concentration to 46% of triple effect evaporation crystallizer subsequently, then concentrated slurry enters crystallisation by cooling in crystallisation by cooling groove, when temperature reaches 27 DEG C, start separating centrifuge, reclaim chloride solid, the mother liquor of 60% is used for the granulation of composite organic-inorganic fertilizer, remain 40% mother liquor and return three-effect evaporation and condensation device.
Gelatin factory phosphorus-containing waste slag slaking: when being 11% by gelatin factory phosphorus-containing waste slag placement natural air drying to moisture, adds vitriol oil adjustment pH and is reached for 5, then place its natural reaction slaking of 3 angels.
Power station straw ash activation: with sulfuric acid, the straw ash in power station is neutralized pH and reach 5, make the K in straw ash
2o is converted into K
2sO
4, medium trace element is converted into water soluble sulfate.
Weathered coal activation treatment: bicarbonate of ammonia is added weathered coal and stirs, places 4 days, makes pH reach 6, improves the activity of Humic Acid from Weathered Coal.
By " three wastes " of the ammonium chloride of above-mentioned recovery and other three kinds of activated process according to ammonium chloride: phosphorus-containing waste slag slaking product: power station straw ash activation products: weathered coal activation products mass ratio equals 0.6:0.15:0.15:0.1 and carries out composite; mixing stirs evenly and sprays into the granulation of ammonium salt mother liquor with rotary conveyor roller pelletizer of making a gift to someone; roller drying machine is sent into after granulating; dry in dryer, finally by sieving, cool, the operation such as packaging is prepared into compound Agricultural Fertilizer.
Claims (1)
1. in recovering rare earth ammonium salt waste water, ammonium chloride prepares a method for agrochemical, it is characterized in that:
(1) recovery of RE waste water ammonium chloride:
A, rare-earth smelting be separated the concentration of discharging be the ammonium salt waste water of 6 ~ 8% first through activated carbon column pre-treatment, make organic concentration in waste water reduce to below 0.5mg/L, then through security personnel filtration devices, to protect aftertreatment device;
B, above-mentioned waste water after pretreatment enter electrodialysis concentrating unit, and ammonium chloride concentration in waste water is promoted to 10 ~ 13%, then adopt HCl that pH in concentrated solution is adjusted to 3 ~ 5;
C, concentrated solution after electrodialysis concentrates enter triple-effect evaporator, and make ammonium chloride be concentrated into 45 ~ 48% further, gained ammonium chloride concentrated slurry enters fertilize preparation craft; Condensation distilled water returns production phase ammonium bicarbonate precipitation technological cycle and uses;
(2) agrochemical is prepared:
A, ammonium salt concentrated solution crystallisation by cooling: step 1 is concentrated into slurries crystallisation by cooling in crystallisation by cooling groove of 45 ~ 48%, when temperature isolates crystallization chloride solid close to putting it into during normal temperature in separating centrifuge, a mother liquor part is used for the granulation of composite organic-inorganic fertilizer, and unnecessary mother liquor returns three-effect evaporation and condensation;
B, the granulation of multielement compound organic and inorganic fertilizer: the waste residue of the ammonia chloride crystal that crystallization in step a is gone out and three kinds of activated process, the required arbitrarily ratio being greater than 60% in ammonium chloride mass concentration carries out compound, stir evenly rear rotary conveyor feeding roller pelletizer and spray into the granulation of ammonium salt mother liquor, roller drying machine is sent into after granulating, dry in dryer, finally by sieving, cool, packaging process makes compound Agricultural Fertilizer;
(3) activating treatment process of three kinds of waste residues described in:
A, gelatin factory phosphorus-containing waste slag activation treatment: placed by gelatin factory phosphorus-containing waste slag, make its natural air drying, when moisture is less than 12%, adds vitriol oil adjustment pH and reach 4 ~ 5.5, place its natural reaction slaking of 1 ~ 3 angel;
B, power station straw ash activate: the straw ash in power station, in alkalescence, is neutralized pH with sulfuric acid and reaches 4.5 ~ 6.5, make the K in straw ash
2o is converted into K
2sO
4, medium trace element is converted into water soluble sulfate;
C, weathered coal activation treatment: bicarbonate of ammonia is added weathered coal and stirs, place 3 ~ 6 days, make pH reach 5 ~ 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410287049.XA CN104071941B (en) | 2014-06-24 | 2014-06-24 | In a kind of recovering rare earth ammonium salt waste water, ammonium chloride prepares the method for agrochemical |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410287049.XA CN104071941B (en) | 2014-06-24 | 2014-06-24 | In a kind of recovering rare earth ammonium salt waste water, ammonium chloride prepares the method for agrochemical |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104071941A CN104071941A (en) | 2014-10-01 |
| CN104071941B true CN104071941B (en) | 2016-03-02 |
Family
ID=51593602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410287049.XA Expired - Fee Related CN104071941B (en) | 2014-06-24 | 2014-06-24 | In a kind of recovering rare earth ammonium salt waste water, ammonium chloride prepares the method for agrochemical |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104071941B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860460A (en) * | 2014-12-05 | 2015-08-26 | 浙江龙盛集团股份有限公司 | Processing device for aniline intermediate production waste water |
| CN104649515B (en) * | 2015-01-16 | 2016-11-30 | 北京交通大学 | The process process of a kind of high salinity height ammonia nitrogen Rare Earth Production waste water and device |
| CN104843925B (en) * | 2015-05-19 | 2017-01-04 | 铜仁市万山区盛和矿业有限责任公司 | Sludge and sewage combined treatment method |
| CN105110541B (en) * | 2015-09-06 | 2017-05-31 | 陕西理工学院 | A kind of low scorification treatment of lead-zinc smelting Wastewater from Acid Preparation and reclaiming system |
| CN106310847A (en) * | 2016-09-14 | 2017-01-11 | 广东电网有限责任公司电力科学研究院 | Oxygen-enriched combustion boiler flue gas purification and resource recycling system and process |
| CN110282799A (en) * | 2019-06-14 | 2019-09-27 | 江苏卓博环保科技有限公司 | The heavy waste water of rare earth carbon and raffinate processing equipment for recycling and method |
| CN110903146A (en) * | 2019-12-13 | 2020-03-24 | 九江天赐高新材料有限公司 | Method for preparing agricultural compound fertilizer by utilizing various waste resources |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007035513A2 (en) * | 2005-09-15 | 2007-03-29 | Vitag Llc | Organic containing sludge to fertilizer alkaline conversion process |
| CN102260002A (en) * | 2011-07-22 | 2011-11-30 | 内蒙古介电电泳应用技术研究院 | Process for treating and recycling rare earth wastewater containing high-concentration sodium chloride and ammonium chloride |
| CN103086551A (en) * | 2013-01-22 | 2013-05-08 | 杭州蓝然环境技术有限公司 | Method for preparing acid-base from rare-earth sodium saponification waste water |
| CN103771642A (en) * | 2014-01-09 | 2014-05-07 | 杭州蓝然环境技术有限公司 | Recycling method for saponified ammonium-sulfate wastewater in rare soil |
-
2014
- 2014-06-24 CN CN201410287049.XA patent/CN104071941B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007035513A2 (en) * | 2005-09-15 | 2007-03-29 | Vitag Llc | Organic containing sludge to fertilizer alkaline conversion process |
| CN102260002A (en) * | 2011-07-22 | 2011-11-30 | 内蒙古介电电泳应用技术研究院 | Process for treating and recycling rare earth wastewater containing high-concentration sodium chloride and ammonium chloride |
| CN103086551A (en) * | 2013-01-22 | 2013-05-08 | 杭州蓝然环境技术有限公司 | Method for preparing acid-base from rare-earth sodium saponification waste water |
| CN103771642A (en) * | 2014-01-09 | 2014-05-07 | 杭州蓝然环境技术有限公司 | Recycling method for saponified ammonium-sulfate wastewater in rare soil |
Non-Patent Citations (1)
| Title |
|---|
| 王俊兰等.对稀土酸法冶炼污染治理的探讨.《内蒙古环境保护》.2003,第15卷(第4期),第19页右栏最后1段，第21页右栏第4.1.2节，图3-2. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104071941A (en) | 2014-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104071941B (en) | In a kind of recovering rare earth ammonium salt waste water, ammonium chloride prepares the method for agrochemical | |
| CN102531025B (en) | Method for treating rare earth ammonium chloride wastewater | |
| CN102249262B (en) | Concentration and cold-precipitation separation method of sodium sulfate and ammonium sulfate from vanadium-precipitation mother liquor high-salt wastewater | |
| CN101337729B (en) | Processing process for fermentation waste liquid of lysine | |
| CN102079601B (en) | Resource recovery and zero discharge process for treating rare-earth wet-method smelting wastewater | |
| CN102864318B (en) | Method for recycling vanadium from acid vanadium-containing solution containing silicon and phosphorus | |
| US11738326B2 (en) | Special pig manure charcoal modified by amino grafting, preparation method thereof, and its application in the reuse of nitrogen from farmland drainage | |
| CN105110352B (en) | A kind of be raw material production potassium sulfate with the solid waste containing potassium, chloride ion method | |
| CN111056682B (en) | Evaporative concentration and sectional crystallization method for RO concentrated solution of landfill leachate | |
| CN102167434A (en) | Method for recovering nitrogen and phosphorous from urine | |
| CN108752059A (en) | Method for producing forest silicon-calcium-manganese composite mineral fertilizer by using manganese slag | |
| CN105367226A (en) | Nanometer organic carbon fertilizer and preparation method thereof | |
| CN107954452B (en) | Brine adding process for mother liquor of potassium chloride production device at low temperature | |
| CN104477943A (en) | Method for preparing potassium sulfate | |
| CN102583916A (en) | Method for removing heavy metal from sludge | |
| CN103539165A (en) | Method for producing potassium sulfate by utilizing insoluble rocks containing potassium | |
| CN103951112A (en) | Method for removing heavy metals in wastewater phosphorus recovery product | |
| CN108569812B (en) | Treatment system and treatment method for wastewater containing low-concentration sulfuric acid | |
| CN106565282A (en) | Production method of high-concentration water-soluble nitrophosphate fertilizer | |
| CN214570788U (en) | High basicity strong brine zero release processing system | |
| CN113072272A (en) | Method for removing heavy metals and recycling phosphorus in municipal sludge | |
| CN102107891A (en) | Method for treating free ammonia during sodium bicarbonate production and application | |
| CN116656952A (en) | Method for treating and recovering manganese, magnesium and ammonium in leachate of electrolytic manganese slag warehouse | |
| CN107417307B (en) | Preparation process of potassium sulfate for water-soluble drip irrigation | |
| CN116199536A (en) | Preparation method of acidic water-soluble composite phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160302 Termination date: 20180624 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |