CN104058525B - Production waste recovery and treatment method containing high ammonia nitrogen and nitric nitrogen - Google Patents
Production waste recovery and treatment method containing high ammonia nitrogen and nitric nitrogen Download PDFInfo
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Abstract
The invention provides a kind of production waste recovery and treatment method containing high ammonia nitrogen and nitric nitrogen, be specifically related to the process alone or in combination containing the production waste of high ammonia nitrogen and nitric nitrogen and the reuse of the discharge of ammonium nitrate, nitric acid ammonia calcium and Nitro Phosphate Unit, adopt reverse osmosis and electrodialytic combined treatment process, with the total salinity of sewage for 5000mg/l is for boundary, sewage lower than this saltiness is introduced into reverse osmosis units process after pre-treatment, and the sewage higher than this saltiness is introduced into electrodialysis cell process.The inventive method ratio of desalinization is high, Water Sproading rate is high, energy consumption is low, cost of investment is low, pollution-free and zero release.
Description
Technical field
The invention belongs to sewage treatment area, especially relates to the process alone or in combination containing the production waste of high ammonia nitrogen and nitric nitrogen and the reuse of the discharge of ammonium nitrate, nitric acid ammonia calcium and Nitro Phosphate Unit.
Background technology
The feature that the production waste of ammonium nitrate, nitric acid ammonia calcium and Nitro Phosphate Unit has is the process condensate being device discharge, all containing NH in sewage
4nO
3, the free ammonia of 1000 ~ 5000mg/L during in alkalescence, can be contained; Unlike, only containing NH in ammonium nitrate sewage
4nO
3and a small amount of free ammonia, and also containing a certain amount of COD, suspended substance and fluorion and other inorganic salt in Phosphate Fertilizer Production sewage, containing calcium ion in nitric acid ammonia calcium production waste.Water-quality constituents is as shown in the table:
The industrial requirement to producing water is:
Fresh water: producing water ratio > 95%, NH
3-N≤10mg/L, TN≤15mg/L
Concentrated solution: producing water ratio < 5%, TDS > 10% (mass percent)
The production waste treatment process of current domestic ammonium nitrate has electroosmose process, reverse osmosis method, electrodialysis+nanofiltration+electrodeionization (EDI) film combined method, ion-exchange AB bed process, conventional biochemical method, ammonia aeration method and break point chlorination.Their respective methods and principle, treatment effect and relative merits see the following form:
Summary of the invention
For solving prior art Problems existing, the present invention is directed to the water quality characteristics of production waste and the water quality requirement of water outlet of ammonium nitrate, nitric acid ammonia calcium and Nitro Phosphate Unit, making full use of reverse osmosis at comparatively low saline salinity (mainly NH
4 +and NO
3 -concentration) time removal advantage, and electrodialysis is at supersalinity (mainly NH
4 +and NO
3 -concentration) time removal advantage, adopt two steps ro+electrodialysis combination process scheme, according to the different saltiness of sewage, select different process combination and sequence, improve ratio of desalinization, reach concentrated solution decrement, the object of fresh water advanced desalination.Producing moisture after process is fresh water and concentrated solution, fresh water producing water ratio can reach more than 95%, water quality can reach the moisturizing water quality requirement of recirculated cooling water in " reuse of wastewater design specifications " completely, and the mixed bed that can be used as recirculating cooling water system moisturizing or Desultwater Station carries out reuse; The concentrated solution water yield is less than 5% of sewage quantity, saltiness 10 ~ 12% (mass percent), and concentrated solution is got back to process unit and reused, and as Nitro Phosphate Unit, realizes real zero release.
The clearance size order of reverse osmosis membrane to common ion is:
Al
3+＞Mg
2+＞Ca
2+＞Na
+＞NH
4 +
PO
4 3-＞SO
4 2-＞Cl
-＞NO
3 -
As can be seen from above-mentioned sequence, NH
4 +, NO
3 -ion is the ion that relative difficult removes, therefore NH in water outlet
3the content of-N and TN is the crucial Con trolling index for the treatment of process, as NH in fresh water production water
4 +, NO
3 -when ion is up to standard, when namely its decreasing ratio need reach more than 90%, the decreasing ratio of other ion is far above this.
Concrete treatment process comprises two large steps:
1. pre-treatment
According to sewage quality, take corresponding pre-treatment measure, adopt the pretreatment mode of heat exchange, neutralization, ozone oxidation and filtration.
The object of heat exchange is that the temperature of water is down to about 20 DEG C the highest to ensure the ratio of desalinization of reverse osmosis units sewage by 55 DEG C.
The object of neutralization ensures to enter the pH of the sewage of reverse osmosis and electrodialysis cell in the scope of 6.5 ~ 8.5, extends the work-ing life of film.According to the pH value of water, Xiang Shuizhong adds nitric acid or ammoniacal liquor adjust ph.
The object of ozone oxidation removes the COD in water, and the dirt reducing film is blocked up.Because the COD in the sewage of Nitro Phosphate Unit is up to 150mg/l, adopts the mode of ozone oxidation, not only can reduce below the COD to 50mg/l in water, in water, do not introduce other ion simultaneously, avoid the difficulty increasing desalination.Sewage after ozone oxidation need carry out precipitation process, removes the suspended substance in water.Settling tank also processes draining and this device land drainage of subsequent filter backwash simultaneously, and oettIed sewage enters filtering unit and continues process, ensures that sewage is without outer row.
The object of filtering removes suspended substance in water and colloid, and ensure the SDI < 4 of the sewage into reverse osmosis or electrodialysis cell, the dirt reducing film is blocked up.Employing more medium filter filters.
2. reverse osmosis and electrodialytic combined treatment process
According to the saltiness of sewage, take 5000mg/l as boundary, the sewage lower than this saltiness is introduced into reverse osmosis units process after pre-treatment, and the sewage higher than this saltiness is introduced into electrodialysis cell process.
Total salinity in the sewage of ammonium nitrate and nitric acid ammonia calcium, all lower than 5000mg/l, therefore after pre-treatment, is all introduced into reverse-osmosis treated.The producing water ratio > 75%, ratio of desalinization > 95%, NH of first step reverse osmosis
4 +and NO
3 -clearance > 90%, the NH of fresh water after first-stage reverse osmosis
4 +concentration < 60mg/l is (with the NH in ammonium nitrate sewage
4 +concentration maxima is 600mg/l meter, the NH in the sewage of nitric acid ammonia calcium
4 +concentration is lower than this value), NO
3 -concentration < 210mg/l is (with the NO in ammonium nitrate sewage
3 -the maximum value of concentration is 2100mg/l meter, the NO in actual nitric acid ammonia calcium sewage
3 -concentration is lower than this value); First-stage reverse osmosis fresh water production water enters two-pass reverse osmosis again and continues desalination, and the ratio of desalinization of second stage reverse osmosis is greater than 90%, NH
4 +and NO
3 -clearance > 88%, the NH of fresh water after two-pass reverse osmosis
3-N concentration < 5.6mg/l (in N), NO
3 --N concentration < 5.7mg/l (in N).The strong brine of two-pass reverse osmosis output enters first-stage reverse osmosis front end and continues process, NH in the strong brine of first-stage reverse osmosis output
4 +concentration > 2400mg/l, NO
3 -concentration > 8400mg/l, enters electrodialysis cell desalination.
Through electrodialysis process, NH
4 +and NO
3 -clearance be greater than 50%, electrodialysis cell dilute side product water is back to first-stage reverse osmosis front end and is separated, the dense water of electrodialysis concentrates at system internal recycle, and when saltiness reaches 10 ~ 12t% (mass percent) left and right, concentrated solution drains into production equipment recycling.The quantity discharged of concentrated solution is lower than 5% of production equipment sewage total amount.
Saltiness in the sewage of nitrophosphate fertilizer is higher than 5000mg/l, and therefore this part sewage is after pre-treatment, is introduced into electrodialysis process.The electrodialytic NH of single-stage
4 +and NO
3 -clearance be greater than 50%, when saltiness of intaking is higher than 9000mg/l, suggestion adopts two-stage electrodialysis series connection process.After two-stage electrodialysis process, the NH in nitrophosphate fertilizer sewage
4 +concentration < 1050mg/l, NO
3 -concentration < 150mg/l; Enter two steps ro cell processing afterwards.The producing water ratio > 75%, ratio of desalinization > 95%, NH of first step reverse osmosis
4 +and NO
3 -clearance > 90%, the NH of fresh water after first-stage reverse osmosis
4 +concentration < 105mg/1, NO
3 -concentration < 15mg/l; First-stage reverse osmosis fresh water production water enters two-pass reverse osmosis again and continues desalination, and the ratio of desalinization of second stage reverse osmosis is greater than 90%, NH
4 +and NO
3 -clearance > 88%, the NH of fresh water after two-pass reverse osmosis
3-N concentration < 9.8mg/l (in N), NO
3 --N concentration < 0.4mg/l (in N).The strong brine of two-pass reverse osmosis output enters first-stage reverse osmosis front end and continues process, NH in the strong brine of first-stage reverse osmosis output
4 +concentration > 6650mg/l, NO
3 -concentration > 950mg/l, is back to electrodialysis cell desalination.When saltiness reaches 10 ~ 12t% (mass percent) left and right, concentrated solution drains into production equipment recycling.The quantity discharged of concentrated solution is lower than 5% of production equipment sewage total amount.
1. equipment or facilities Allocation and type selecting explanation
1. reverse osmosis membrane suggestion adopts 34mil major path pollution-resistant, and material is aromatic polyamide membrane.
2. electrodialysis cell suggestion adopts homogeneous membrane, and membrane resistance is little, and porosity is little, not easy to leak, regularly pole, automatically the dirt that formed of cleaning ion-exchange membrane and electrode surface, with the water quality of the permanent stability and fresh water of guaranteeing ion-exchange membrane ratio of desalinization and the water yield.
3. after production waste recovery, the fresh water water quality of output can reach: NH
3-N concentration < 10mg/l (in N), TN concentration < 15mg/l (in N); Fresh water can be used for circulating cooling make-up water or the water inlet of Desultwater Station mixed bed; As the reuse of high-quality de-salted water, electrodeionization unit (EDI) or mixed bed unit continuation advanced treatment also need can be arranged after two-pass reverse osmosis.
4. as saltiness (or the NH of Nitro Phosphate Unit production waste
4 +, NO
3 -content) high (as being greater than 9000mg/l) time, the mode that also two-stage electrodialysis cell can be adopted to connect improves ratio of desalinization and producing water ratio, ensures final product water water quality and quantity requirement.
2., for the process alone or in combination containing the production waste of high ammonia nitrogen and nitric nitrogen and the reuse of the discharge of ammonium nitrate, nitric acid ammonia calcium and Nitro Phosphate Unit, adopt following several allocation plan to process:
For the production waste of nitrophosphate fertilizer, ammonium nitrate and nitric acid ammonia calcium device, can process respectively according to above-mentioned treatment process, also can merging treatment.Should note during merging treatment:
1. F is contained in Phosphate Fertilizer Production sewage
-, and containing Ca in nitric acid ammonia calcium production waste
2+, therefore the production waste of nitrophosphate fertilizer and nitric acid ammonia calcium should process respectively.
2. nitric acid ammonia calcium is similar with the production waste component of ammonium nitrate plant, can not form precipitation, and saltiness is all less than 5000mg/L after mixing, and therefore the production waste of nitric acid ammonia calcium and ammonium nitrate plant can merging treatment.
3. the wastewater composition of ammonium nitrate plant is relatively simple, mainly NO
3 -and NH
4 +also containing above-mentioned two kinds of ions in Nitro Phosphate Unit production waste, therefore the production waste of ammonium nitrate plant also can with Nitro Phosphate Unit production waste merging treatment, but because the saltiness in Nitro Phosphate Unit production waste is very high, about about 8000 ~ 18000mg/L, and the saltiness in ammonium nitrate production sewage is less than 3000mg/L, therefore, as needed merging treatment, the production waste of ammonium nitrate plant should merge with the Nitro Phosphate Unit production waste after electrodialysis process and enters reverse osmosis units and process.
Utilize the sewage of the art of this patent treatment of nitric acid ammonium, nitric acid ammonia calcium and Nitro Phosphate Unit compared with the treatment process of existing ammonium nitrate plant sewage, there is following features:
1. ratio of desalinization is high
Compared with existing pure electrodialysis process technique, because reverse osmosis+electrodialysis process scheme has given full play to the desalination advantage of two kinds of desalting technologies under different saltiness condition; Adopt the art of this patent ratio of desalinization greatly to improve, the effluent quality of fresh water can close to de-salted water standard, can be used as circulating cooling make-up water or the former water of Desultwater Station mixed bed carries out reuse.
2. Water Sproading rate is high
Compared with existing ro treatment technology, because electrodialysis has incomparable advantage to high-concentration sewage concentrate, therefore by the dense water of the reverse osmosis further separating and concentrating of electrodialytic mode, dense water saltiness can be concentrated into more than 12% (mass percent), and the dense water yield can reduce to less than 5%.
3. energy consumption is low
Electrodialysis process low saline salinity sewage efficiency is low, and energy consumption is high; Reverse-osmosis treated supersalinity sewage ratio of desalinization is low, and dense aquatic products amount is large; Adopt the reverse osmosis+electrodialytic technique of this patent, greatly reduce than simple electrodialysis or the reverse osmosis desalination energy consumption of adopting, running cost is lower.
4. cost of investment is low
Reverse osmosis+electrodialysis process ratio of desalinization is high, compared with pure electrodialysis, reverse osmosis unit or electrodialysis+nanofiltration+electrodeionization combined method, number of devices reduces, and the cost of investment of reverse osmosis is lower than the cost of investment of other treatment facility, reverse osmosis+electrodialytic treatment process is therefore adopted to reduce the cost of investment of whole treatment system.And system cloud gray model is more stable, operate easier, safe and reliable.
5. pollution-free, zero release
Compared with A/B bed process, reverse osmosis+electrodialysis process is without the need to regeneration, and without the secondary treatment of regenerated sewage, concentrated solution is all back to process unit recycling, achieves recovery and the zero release of resource.
Accompanying drawing explanation
Fig. 1 is nitrophosphate fertilizer sewage treatment process schematic diagram
Fig. 2 is nitric acid ammonia calcium sewage treatment process schematic diagram
Fig. 3 is nitric acid ammonia sewage device processing technological flow schematic diagram
Embodiment
Elaborate below in conjunction with the specific embodiment of accompanying drawing to the invention.
1, nitrophosphate fertilizer sewage treatment process
(1) pre-treatment
High for Nitro Phosphate Unit production waste temperature, feature containing a small amount of COD and SS, adopt the pretreatment technology of heat exchange+precipitation+chemical oxidation+filtration, sewage first enters ozone oxidation pond after plate-type heat exchanger is cooled to 20 DEG C, water outlet overflow is to perpendicular stream settling bowl, deliver to sewage regulating tank after clarification to store, then promote through pump and enter strainer and to remove in water suspended substance etc., ensure water outlet SDI < 4.The backwash water lift pump of strainer is delivered to the process of perpendicular stream settling bowl.
(2) desalination and concentration
Strainer produces water and directly enters electrodialysis, and it is 12% (mass percent) left and right that dense water is concentrated into concentration through electrodialysis cell circulation, is stored in concentrated solution case and through being pumped to Nitro Phosphate Unit recycle.Fresh water ratio of desalinization after the electrodialysis cell desalination of two-stage series connection reaches about 75%, and fresh water outlet continues desalination through two steps ro again, two-pass reverse osmosis fresh water production water NH
3-N≤10mg/L, TN≤15mg/L.The dense water of two-pass reverse osmosis is back to the front end desalination again of first-stage reverse osmosis.The dense water of first-stage reverse osmosis is delivered to electrodialysis cell and is processed.
2, nitric acid ammonia calcium sewage treatment process
(1) pre-treatment
For the feature that nitric acid ammonia calcium device production waste temperature is high, adopt the pretreatment technology of heat exchange+filtration, sewage first enters regulating tank after plate-type heat exchanger is cooled to 20 DEG C, promote with pump again and enter strainer and remove colloid in water and particulate matter etc., ensure strainer water outlet SDI < 4.The backwash water lift pump of strainer is delivered to vertical-flow settling bowl process.Vertical-flow settling bowl water outlet flows in regulating tank and stores.
(2) desalination and concentration
Strainer produces water and directly enters two steps ro desalination, two-pass reverse osmosis fresh water production water NH
3-N≤10mg/L, TN≤15mg/L.The dense water of two-pass reverse osmosis is back to the front end desalination again of first-stage reverse osmosis.The dense water of first-stage reverse osmosis is delivered to electrodialysis cell and is processed.It is 12% (mass percent) left and right that dense water is concentrated into concentration through electrodialysis cell circulation, is stored in concentrated solution case and through being pumped to Nitro Phosphate Unit recycle.Dilute side ratio of desalinization after electrodialysis cell desalination reaches about 50%, and fresh water is back to reverse osmosis front end again and continues desalination.
3, nitric acid ammonia sewage device processing technological flow
(1) pre-treatment
Ammonium nitrate plant production waste water quality is better, the NH only containing about 2000mg/l
4nO
3, without other impurity, therefore can directly deliver to reverse osmosis units desalination after heat exchange cooling.
(2) desalination and concentration
Ammonium nitrate sewage after cooling directly enters two steps ro desalination, two-pass reverse osmosis fresh water production water NH
3-N≤10mg/L, TN≤15mg/L.The dense water of two-pass reverse osmosis is back to the front end desalination again of first-stage reverse osmosis.The dense water of first-stage reverse osmosis is delivered to electrodialysis cell and is processed.It is 12% (mass percent) left and right that dense water is concentrated into concentration through electrodialysis cell circulation, is stored in concentrated solution case and through being pumped to Nitro Phosphate Unit recycle.Dilute side ratio of desalinization after electrodialysis cell desalination reaches about 50%, and fresh water is back to reverse osmosis front end again and continues desalination.
Application case:
The ammonium nitrate of certain phosphatization project, nitric acid ammonia calcium and Nitro Phosphate Unit production waste treatment station:
Sewage water quantity and quality:
Processing scheme: Phosphate Fertilizer Production sewage and nitric acid ammonia calcium production waste process respectively, the production waste of a part of ammonium nitrate plant and pretreated nitric acid ammonia calcium sewage merging treatment, another part and Phosphate Fertilizer Production sewage merging treatment.
Effluent quality and the water yield:
Fresh water: 26.3 ~ 29.6m
3/ h, ammonia nitrogen NH
3-N < 10mg/l, total nitrogen T-N < 15mg/l
Dense water: 1.6 ~ 1.7m
3/ h, saltiness > 10% (mass percent)
Fresh water reuse is to Desultwater Station as moisturizing, and dense water is back to Nitro Phosphate Unit as production water.
Above an embodiment of the invention has been described in detail, but described content being only the preferred embodiment of the invention, the practical range for limiting the invention can not being considered to.All equalization changes done according to the invention application range with improve, within the patent covering scope that still all should belong to the invention.
Claims (6)
1. contain the production waste recovery and treatment method of high ammonia nitrogen and nitric nitrogen, it is characterized in that: adopt reverse osmosis and electrodialytic combined treatment process, with the total salinity of sewage for 5000mg/l is for boundary, sewage lower than this saltiness is introduced into reverse osmosis units process after pre-treatment, and the sewage higher than this saltiness is introduced into electrodialysis cell process;
When total salinity in the sewage of ammonium nitrate and nitric acid ammonia calcium is all lower than 5000mg/l, after pre-treatment, be all introduced into reverse-osmosis treated; The producing water ratio > 75%, ratio of desalinization > 95%, NH of first step reverse osmosis
4 +and NO
3 -clearance > 90%, the NH of fresh water after first-stage reverse osmosis
4 +concentration < 60mg/l, NO
3 -concentration < 210mg/l; First-stage reverse osmosis fresh water production water enters two-pass reverse osmosis again and continues desalination, and the ratio of desalinization of second stage reverse osmosis is greater than 90%, NH
4 +and NO
3 -clearance > 88%, the NH of fresh water after two-pass reverse osmosis
3-N concentration is in N < 5.6mg/l, NO
3 --N concentration is in N < 5.7mg/l; The strong brine of two-pass reverse osmosis output enters first-stage reverse osmosis front end and continues process, NH in the strong brine of first-stage reverse osmosis output
4 +concentration > 2400mg/l, NO
3 -concentration > 8400mg/l, enters electrodialysis cell desalination;
Through electrodialysis process, NH
4 +and NO
3 -clearance be greater than 50%, electrodialysis cell dilute side is produced water and is back to first-stage reverse osmosis front end and is separated, and the dense water of electrodialysis concentrates at system internal recycle, and when saltiness mass percent reaches 10 ~ 12t%, concentrated solution drains into production equipment recycling; The quantity discharged of concentrated solution is lower than 5% of production equipment sewage total amount;
When saltiness in the sewage of nitrophosphate fertilizer is higher than 5000mg/l, this part sewage, after pre-treatment, is introduced into electrodialysis process; The electrodialytic NH of single-stage
4 +and NO
3 -clearance be greater than 50%, after electrodialysis process, the NH in nitrophosphate fertilizer sewage
4 +concentration < 1050mg/l, NO
3 -concentration < 150mg/l; Enter two steps ro cell processing afterwards; The producing water ratio > 75%, ratio of desalinization > 95%, NH of first step reverse osmosis
4 +and NO
3 -clearance > 90%, the NH of fresh water after first-stage reverse osmosis
4 +concentration < 105mg/l, NO
3 -concentration < 15mg/l; First-stage reverse osmosis fresh water production water enters two-pass reverse osmosis again and continues desalination, and the ratio of desalinization of second stage reverse osmosis is greater than 90%, NH
4 +and NO
3 -clearance > 88%, the NH of fresh water after two-pass reverse osmosis
3-N concentration is in N < 9.8mg/l, NO
3 --N concentration is in N < 0.4mg/l; The strong brine of two-pass reverse osmosis output enters first-stage reverse osmosis front end and continues process, NH in the strong brine of first-stage reverse osmosis output
4 +concentration > 6650mg/l, NO
3 -concentration > 950mg/l, is back to electrodialysis cell desalination.
2. the production waste recovery and treatment method containing high ammonia nitrogen and nitric nitrogen according to claim 1, is characterized in that: when the saltiness in the sewage of nitrophosphate fertilizer is higher than 9000mg/l, adopts two-stage electrodialysis series connection process.
3. the production waste recovery and treatment method containing high ammonia nitrogen and nitric nitrogen according to claim 1, it is characterized in that: according to sewage quality, take corresponding pre-treatment measure, described pre-treatment comprises one or more combinations in heat exchange, neutralization, ozone oxidation, filtration.
4. the production waste recovery and treatment method containing high ammonia nitrogen and nitric nitrogen according to claim 1, is characterized in that: reverse osmosis membrane adopts 34mil major path pollution-resistant, and material is aromatic polyamide membrane; Electrodialysis cell adopts homogeneous membrane.
5. the production waste recovery and treatment method containing high ammonia nitrogen and nitric nitrogen according to claim 1, is characterized in that: after production waste reclaims, the fresh water water quality of output is: NH
3-N concentration is in N < 10mg/l, and TN concentration is in N < 15mg/l; Fresh water can be used for circulating cooling make-up water or the water inlet of Desultwater Station mixed bed; As need as the reuse of high-quality de-salted water time, electrodeionization unit or mixed bed unit are set after two-pass reverse osmosis and continue advanced treatment.
6. the production waste recovery and treatment method containing high ammonia nitrogen and nitric nitrogen according to claim 1, is characterized in that: the production waste for nitrophosphate fertilizer, nitric acid ammonia calcium, ammonium nitrate plant adopts following several allocation plan to process:
(1) production waste of nitrophosphate fertilizer and nitric acid ammonia calcium device should process respectively;
(2) production waste of nitric acid ammonia calcium and ammonium nitrate plant can merging treatment;
(3), when the production waste of ammonium nitrate and Nitro Phosphate Unit needs merging treatment, the production waste of ammonium nitrate plant should merge with the Nitro Phosphate Unit production waste after electrodialysis process and enters reverse osmosis units and process.
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| CN104529008B (en) * | 2014-12-30 | 2016-08-17 | 中国天辰工程有限公司 | A kind of containing fluorine phosphorus sewage disposal system for Phosphate Fertilizer Production technique and process technique |
| CN107500446A (en) * | 2016-06-14 | 2017-12-22 | 贵州芭田生态工程有限公司 | The processing system and processing method of Phosphate Fertilizer Production waste water |
| CN106587450A (en) * | 2016-12-15 | 2017-04-26 | 贵州芭田生态工程有限公司 | Treatment system and treatment method for calcium ammonium nitrate production wastewater |
| CN110467941A (en) * | 2019-08-20 | 2019-11-19 | 山东京博石油化工有限公司 | A kind of processing method and system of crude oil electric desalting draining |
| CN111439863A (en) * | 2020-03-31 | 2020-07-24 | 山东聊城鲁西硝基复肥有限公司 | Calcium ammonium nitrate production wastewater treatment system and process |
| CN115611462A (en) * | 2022-10-21 | 2023-01-17 | 江苏博辰环保科技有限公司 | Method for recovering and treating calcium ammonium nitrate and ammonium nitrate condensation wastewater |
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| CN104058525A (en) | 2014-09-24 |
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