CN102557212B - Method for treating and recycling molybdenum calcine water-washing waste water - Google Patents
Method for treating and recycling molybdenum calcine water-washing waste water Download PDFInfo
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Abstract
The invention discloses a method for treating and recycling molybdenum calcine water-washing waste water. In the method, molybdenum calcine water-washing waste water and an acid precipitation crystalized mother liquor produced in an ammonium molybdate production process are mixed in the volume ratio of 1:(0.5-5), and molybdenum in the molybdenum calcine water-washing waste water and molybdenum in the acid precipitation crystalized mother liquor are precipitated for recycling. In the method, water-washing and acid precipitation molybdenum-containing waste water is treated by adopting a unique mixed precipitation method, molybdenum in waste water is precipitated through mixed precipitation for recycling conveniently, a filtrate is returned to an acid washing procedure simultaneously, and acid-washed waste water meets an environmental protection requirement after being treated through the conventional waste water treatment system. The method is used for comprehensively treating two types of waste water at one time, and has the characteristics of small equipment investment, low material consumption, easiness for operating, wide adaptation, and the like.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to a kind of method that molybdenum calcining washing waste water is processed recycling.
Background technology
Adopt in tradition preparation production of molybdic ammonium that pickling molybdenum calcining, ammonia soak, acid sink, ammonia is molten, evaporative crystallization is prepared into ammonium dimolybdate, in this art production process at pickling and a large amount of acid ammonia nitrogen waste waters of the heavy meeting generation of acid, serious environment pollution.Environmental protection production ammonium dimolybdate technique is imperative.Employing washing molybdenum calcining is produced ammonium dimolybdate technique and can be solved the problem of ammonia and nitrogen pollution, but finds in this process implementing process, and it is higher that the waste water that washing molybdenum calcining produces contains the molybdenum amount, on average can reach about 10g/L～30g/L, and the pH value is in 3～4 left and right.Because the existing calcining molybdenum concentrate quality level of China is generally lower, mostly adopt existing technique pickling molybdenum calcining to produce ammonium tetramolybdate technique except heteroacid is heavy in addition.Therefore it is imperative that the waste water that the waste water that washing molybdenum calcining is produced and the heavy crystalline mother solution of acid and pickling molybdenum calcining produce carries out comprehensive treating process.Be ion-exchange and extraction process for the traditional method of the recovery of molybdenum in waste liquid, but these two kinds all exist environmental protection and long processing period, the problems such as regeneration difficulty.Although nanofiltration membrane treatment technique has stronger pressure tightness and stronger stain resistance and charge, can separate with high valence ion the low price ion, but also exist membrane washing frequent, the shortcoming that the life-span is long, the condensed water of washing waste water after concentrating needs further to process in addition.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of molybdenum calcining washing waste water to process the method for recycling.The present invention is according to the characteristics of washing waste water and the heavy crystalline mother solution of acid, suitably regulate the pH value, in the situation that do not add other precipitation agents that molybdenum is precipitated with forms such as isopoly-acid salt and double salt, reach the purpose of two kinds of comprehensive primary treatments of waste water, has facility investment little, the characteristics such as consumptive material is few, and is simple to operate, scalable.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of molybdenum calcining washing waste water is processed the method for recycling, it is characterized in that, the method is that the heavy crystalline mother solution of the acid in molybdenum calcining washing waste water and production of molybdic ammonium process is mixed by 1: 0.5～5 volume ratio, makes molybdenum in molybdenum calcining washing waste water and the molybdenum in the heavy crystalline mother solution of acid form the precipitation recycling.
Above-mentioned molybdenum calcining washing waste water is processed the method for recycling, and the method comprises the following steps:
Step 1, stir after the heavy crystalline mother solution of the acid in molybdenum calcining washing waste water and production of molybdic ammonium process is mixed by 1: 0.5～5 volume ratio, then regulating the pH value is 1.0～4.0, and continuation stirring 10min～60min obtains solidliquid mixture;
Step 2, solidliquid mixture described in step 1 is carried out solid-liquid separation, the filter cake that separation is obtained is sent into and is carried out ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, the filtrate that separation is obtained is sent into the molybdenum calcining pickling process of production of molybdic ammonium technique and is recycled, and realizes the recycling of Recycle of molybdenum and waste water in molybdenum calcining washing waste water.
Above-mentioned molybdenum calcining washing waste water is processed the method for recycling, and the equipment that solid-liquid separation described in step 2 adopts is plate-and-frame filter press.
Above-mentioned molybdenum calcining washing waste water is processed the method for recycling, described in step 2 in filtrate molybdenum content be not more than 1.5g/L.
Above-mentioned molybdenum calcining washing waste water is processed the method for recycling, it is 70 ℃～100 ℃ that filtrate described in step 2 enters the temperature of carrying out cleanup acid treatment in molybdenum calcining pickling process, the pH value is 0.5～2.5, and liquid-solid ratio is 2～5: 1, and the cleanup acid treatment time is 1h～3h.
Above-mentioned molybdenum calcining washing waste water is processed the method for recycling, the method also comprises carries out solid-liquid separation to the slurry after cleanup acid treatment, the filter cake that separation is obtained is sent into and is carried out ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, and the filtrate that separation is obtained is sent into and processed rear discharging up to standard in Waste Water Treatment.
Above-mentioned molybdenum calcining washing waste water is processed the method for recycling, the method is: obtain slurry with stirring after the heavy crystalline mother solution of the acid in molybdenum calcining washing waste water, production of molybdic ammonium process and calcining molybdenum concentrate mixing, the pH value of regulating slurry is 0.5～2.5, then under temperature is the condition of 70 ℃～100 ℃, slurry is stirred 1h～3h and carries out cleanup acid treatment; Slurry after cleanup acid treatment is carried out solid-liquid separation, and the filter cake that separation is obtained is sent into and is carried out ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, and the filtrate that separation is obtained is sent into and processed rear discharging up to standard in Waste Water Treatment; The volume ratio of the heavy crystalline mother solution of the acid in described molybdenum calcining washing waste water and production of molybdic ammonium process is 1: 0.5～5, and the liquid-solid ratio of described slurry is 2～5: 1.
Above-mentioned molybdenum calcining washing waste water is processed the method for recycling, and in described filtrate, molybdenum content is not more than 0.5g/L.
Above-mentioned molybdenum calcining washing waste water is processed the method for recycling, and the equipment that described solid-liquid separation adopts is plate-and-frame filter press.
The present invention compared with prior art has the following advantages:
1, the present invention is according to the characteristics of washing waste water and the heavy crystalline mother solution of acid, suitably regulate the pH value, in the situation that do not add other precipitation agents that molybdenum is precipitated with forms such as isopoly-acid salt and double salt, reach the purpose of two kinds of comprehensive primary treatments of waste water, has facility investment little, the characteristics such as consumptive material is few, and is simple to operate, scalable.
2, the present invention adopts unique mixed precipitation method to process washing, the heavy wastewater containing molybdenum of acid, make molybdenum precipitation in waste water by mixed precipitation, be convenient to reclaim, simultaneously filtrate returned to pickling process, the waste water after pickling is meet the requirement of environmental protection after conventional Waste Water Treatment is processed.
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment
Embodiment 1
The molybdenum calcining washing waste water pH value of the present embodiment is 3～4, and in waste water, each ionic concn is: molybdenum 24.29g/L, copper 0.5g/L, iron 0.74g/L, potassium 0.8g/L, sodium 0.028g/L, calcium 0.21g/L, magnesium 0.35g/L; The heavy crystalline mother solution pH value of acid is 5, and each indicator ion is: molybdenum 15.74g/L, copper 0.004g/L, iron 0.0026g/L, potassium 0.076g/L, sodium 0.17g/L, calcium 0.015g/L, magnesium 0.024g/L.
The method that the molybdenum calcining washing waste water of the present embodiment is processed recycling is:
Step 1, after being mixed by the volume ratio of 1: 2.5, the heavy crystalline mother solution of the acid in molybdenum calcining washing waste water and production of molybdic ammonium process stirs, then using nitric acid (also available other acid substitutions) to regulate the pH value is 2.5, continue to stir 30min, obtain solidliquid mixture;
Step 2, employing plate-and-frame filter press carry out solid-liquid separation to solidliquid mixture described in step 1, filter cake and filtrate that separation obtains are detected, the chemical index of filter cake (wt%) is: molybdenum 52.2%, copper 0.016%, iron 0.55%, potassium 0.029%, sodium 0.004%, calcium 0.0065%, magnesium 0.0018%; The pH value of filtrate is 2.5, and in filtrate, each ionic concn is: molybdenum 1.5g/L, copper 0.15g/L, iron 0.093g/L, potassium 0.16g/L, sodium 0.11g/L, calcium 0.10g/L, magnesium 0.14g/L.
Embodiment 2
The filter cake that embodiment 1 is obtained is sent into and is carried out conventional ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing; The filtrate that embodiment 1 obtains is sent in the molybdenum calcining pickling process of production of molybdic ammonium technique, calcining molybdenum concentrate is carried out cleanup acid treatment, and the temperature of cleanup acid treatment is 90 ℃, and the pH value is 0.5～1, liquid-solid ratio (mass ratio of filtrate and calcining molybdenum concentrate) is 3: 1, and the cleanup acid treatment time is 1h; Then the slurry after adopting plate-and-frame filter press to cleanup acid treatment carries out solid-liquid separation, and the filter cake that separation is obtained is sent into and carried out ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, and the filtrate that separation is obtained is sent into and processed rear discharging up to standard in Waste Water Treatment.
In the calcining molybdenum concentrate of the present embodiment, the mass content of molybdenum is 63.03%, and the mass content of copper is 0.13%, and the mass content of the insoluble molybdenum of ammonia is 0.74%; The chemical index (wt%) of the filter cake that obtains after the filtrate pickling of embodiment 1 is: molybdenum 62.6%, copper 0.005%, iron 0.97%, potassium 0.032%, sodium 0.004%, calcium 0.12%, magnesium 0.0083%; The pH value of the filtrate that obtains is 2.5, and in filtrate, each ionic concn is: molybdenum 1.06g/L, copper 0.86g/L, iron 0.6g/L, potassium 0.82g/L, sodium 0.07g/L, calcium 0.4g/L, magnesium 0.23g/L.
Embodiment 3
The molybdenum calcining washing waste water pH value of the present embodiment is 3～4, and in waste water, each ionic concn is: molybdenum 26.64g/L, copper 0.96g/L, iron 0.029g/L, potassium 0.68g/L, sodium 0.027g/L, calcium 0.026g/L, magnesium 0.03g/L; The heavy crystalline mother solution pH value of acid is 2.5, and each indicator ion is: molybdenum 15g/L, copper 0.016g/L, iron 1.52g/L, potassium 0.056g/L, sodium 0.15g/L, calcium 0.24g/L, magnesium 0.34g/L.
The method that the molybdenum calcining washing waste water of the present embodiment is processed recycling is:
Step 1, after being mixed by the volume ratio of 1: 0.5, the heavy crystalline mother solution of the acid in molybdenum calcining washing waste water and production of molybdic ammonium process stirs, then using nitric acid (also available other acid substitutions) to regulate the pH value is 1.0, continue to stir 60min, obtain solidliquid mixture;
Step 2, employing plate-and-frame filter press carry out solid-liquid separation to solidliquid mixture described in step 1, filter cake and filtrate that separation obtains are detected, the chemical index of filter cake (wt%) is: molybdenum 48.2%, copper 0.021%, iron 0.64%, potassium 0.07%, sodium 0.009%, calcium 0.029%, magnesium 0.0077%; The pH value of filtrate is 1.5, and in filtrate, each ionic concn is: molybdenum 1.2g/L, copper 0.63g/L, iron 0.41g/L, potassium 0.63g/L, sodium 0.087g/L, calcium 0.19g/L, magnesium 0.23g/L.
Embodiment 4
The filter cake that embodiment 3 is obtained is sent into and is carried out conventional ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing; The filtrate that embodiment 3 obtains is sent in the molybdenum calcining pickling process of production of molybdic ammonium technique, calcining molybdenum concentrate is carried out cleanup acid treatment, and the temperature of cleanup acid treatment is 100 ℃, and the pH value is 2～2.5, liquid-solid ratio (mass ratio of filtrate and calcining molybdenum concentrate) is 2: 1, and the cleanup acid treatment time is 2h; Then the slurry after adopting plate-and-frame filter press to cleanup acid treatment carries out solid-liquid separation, and the filter cake that separation is obtained is sent into and carried out ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, and the filtrate that separation is obtained is sent into and processed rear discharging up to standard in Waste Water Treatment.
In the calcining molybdenum concentrate of the present embodiment, the mass content of molybdenum is 63.03%, and the mass content of copper is 0.13%, and the mass content of the insoluble molybdenum of ammonia is 0.74%; The chemical index (wt%) of the filter cake that obtains after the filtrate pickling of embodiment 3 is: molybdenum 61.8%, copper 0.004%, iron 1.05%, potassium 0.027%, sodium 0.004%, calcium 0.12%, magnesium 0.0085%; The pH value of filtrate is 2.0, and in filtrate, each ionic concn is: molybdenum 1.98g/L, copper 0.80g/L, iron 0.24g/L, potassium 0.60g/L, sodium 0.12g/L, calcium 0.33g/L, magnesium 0.35g/L.
Embodiment 5
The molybdenum calcining washing waste water pH value of the present embodiment is 3～4, and in waste water, each ionic concn is: molybdenum 37.63g/L, copper 0.6g/L, iron 2.08mg/L, potassium 0.26g/L, sodium 0.052mg/L, calcium 0.46mg/L; The heavy crystalline mother solution pH value of acid is 5, and each indicator ion is: molybdenum 22.8g/L, copper 0.6g/L, iron 0.0026g/L, potassium 0.074g/L, sodium 0.16g/L, calcium 0.0138g/L, magnesium 0.03095g/L.
The method that the molybdenum calcining washing waste water of the present embodiment is processed recycling is:
Step 1, after being mixed by the volume ratio of 1: 5, the heavy crystalline mother solution of the acid in molybdenum calcining washing waste water and production of molybdic ammonium process stirs, then using nitric acid (also available other acid substitutions) to regulate the pH value is 4.0, continue to stir 10min, obtain solidliquid mixture;
Step 2, employing plate-and-frame filter press carry out solid-liquid separation to solidliquid mixture described in step 1, filter cake and filtrate that separation obtains are detected, the chemical index of filter cake (wt%) is: molybdenum 49.6%, copper 0.022%, iron 0.64%, potassium 0.048%, sodium 0.038%, calcium 0.039%, magnesium 0.0067%; The pH value of filtrate is 4.0, and in filtrate, each ionic concn is: molybdenum 1.44g/L, copper 0.17g/L, iron 0.51g/L, potassium 0.27g/L, sodium 0.15g/L, calcium 0.29g/L, magnesium 0.023g/L.
Embodiment 6
The filter cake that embodiment 5 is obtained is sent into and is carried out conventional ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing; The filtrate that embodiment 5 obtains is sent in the molybdenum calcining pickling process of production of molybdic ammonium technique, calcining molybdenum concentrate is carried out cleanup acid treatment, and the temperature of cleanup acid treatment is 70 ℃, and the pH value is 1～1.5, liquid-solid ratio (mass ratio of filtrate and calcining molybdenum concentrate) is 5: 1, and the cleanup acid treatment time is 3h; Then the slurry after adopting plate-and-frame filter press to cleanup acid treatment carries out solid-liquid separation, and the filter cake that separation is obtained is sent into and carried out ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, and the filtrate that separation is obtained is sent into and processed rear discharging up to standard in Waste Water Treatment.
In the calcining molybdenum concentrate of the present embodiment, the mass content of molybdenum is 63.03%, and the mass content of copper is 0.13%, and the mass content of the insoluble molybdenum of ammonia is 0.74%; The chemical index (wt%) of the filter cake that obtains after the filtrate pickling of embodiment 5 is: molybdenum 48.2%, copper 0.021%, iron 0.64%, potassium 0.07%, sodium 0.009%, calcium 0.029%, magnesium 0.0077%; The pH value of filtrate is 1.5, and in filtrate, each ionic concn is: molybdenum 1.2g/L, copper 0.63g/L, iron 0.41g/L, potassium 0.63g/L, sodium 0.087g/L, calcium 0.19g/L, magnesium 0.23g/L.
Embodiment 7
The molybdenum calcining washing waste water pH value of the present embodiment is 3～4, and in waste water, each ionic concn is: molybdenum 37.63g/L, copper 0.6g/L, iron 2.08g/L, potassium 0.26g/L, sodium 0.052g/L, calcium 0.46g/L; The heavy crystalline mother solution pH value of acid is 5, and each indicator ion is: molybdenum 22.8g/L, copper 0.6g/L, iron 0.0026g/L, potassium 0.074g/L, sodium 0.16g/L, calcium 0.0138g/L, magnesium 0.03095g/L; In calcining molybdenum concentrate, the mass content of molybdenum is 63.03%, and the mass content of copper is 0.13%, and the mass content of the insoluble molybdenum of ammonia is 0.74%.
The method that the molybdenum calcining washing waste water of the present embodiment is processed recycling is:
Stir after molybdenum calcining washing waste water, the heavy crystalline mother solution of acid and calcining molybdenum concentrate are mixed and obtain slurry, the pH value of regulating slurry with nitric acid (also available other acid substitutions) is 0.5, then under temperature is the condition of 90 ℃, slurry is stirred 1h and carries out cleanup acid treatment; Adopt plate-and-frame filter press to carry out solid-liquid separation to the slurry after cleanup acid treatment, the filter cake that separation is obtained is sent into and is carried out conventional ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, and the filtrate that separation is obtained is sent into and processed rear discharging up to standard in Waste Water Treatment; The volume ratio of the heavy crystalline mother solution of the acid in described molybdenum calcining washing waste water and production of molybdic ammonium process is 1: 0.5, and the liquid-solid ratio of described slurry is 3: 1.
The present embodiment is separated the filtrate and the filter cake that obtain detect, the chemical index of filter cake (wt%) is: molybdenum 61.6%, copper 0.016%, iron 0.69%, potassium 0.018%, sodium 0.005%, calcium 0.051%, magnesium 0.011%; The pH value of filtrate is 1.0, and in filtrate, each ionic concn is: molybdenum 0.38g/L, copper 0.5g/L, iron 0.093g/L, potassium 0.26g/L, sodium 0.11g/L, calcium 0.45g/L, magnesium 0.35g/L.
Embodiment 8
The molybdenum calcining washing waste water pH value of the present embodiment is 3～4, and in waste water, each ionic concn is: molybdenum 26.64g/L, copper 0.96g/L, iron 0.029g/L, potassium 0.68g/L, sodium 0.027g/L, calcium 0.026g/L, magnesium 0.03g/L; The heavy crystalline mother solution pH value of acid is 2.5, and each indicator ion is: molybdenum 15g/L, copper 0.016g/L, iron 1.52g/L, potassium 0.056g/L, sodium 0.15g/L, calcium 0.24g/L, magnesium 0.34g/L; In calcining molybdenum concentrate, the mass content of molybdenum is 63.03%, and the mass content of copper is 0.13%, and the mass content of the insoluble molybdenum of ammonia is 0.74%.
The method that the molybdenum calcining washing waste water of the present embodiment is processed recycling is:
Stir after molybdenum calcining washing waste water, the heavy crystalline mother solution of acid and calcining molybdenum concentrate are mixed and obtain slurry, the pH value of regulating slurry with nitric acid (also available other acid substitutions) is 1.0, then under temperature is the condition of 70 ℃, slurry is stirred 3h and carries out cleanup acid treatment; Adopt plate-and-frame filter press to carry out solid-liquid separation to the slurry after cleanup acid treatment, the filter cake that separation is obtained is sent into and is carried out conventional ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, and the filtrate that separation is obtained is sent into and processed rear discharging up to standard in Waste Water Treatment; The volume ratio of the heavy crystalline mother solution of the acid in described molybdenum calcining washing waste water and production of molybdic ammonium process is 1: 5, and the liquid-solid ratio of described slurry is 2: 1.
The present embodiment is separated the filtrate and the filter cake that obtain detect, the chemical index of filter cake (wt%) is: molybdenum 62.40%, copper 0.011%, iron 1.20%, potassium 0.050%, sodium 0.005%, calcium 0.104%, magnesium 0.010%; The pH value of filtrate is 1.5, and in filtrate, each ionic concn is: molybdenum 0.50g/L, copper 0.65g/L, iron 0.00013g/L, potassium 0.66g/L, sodium 0.084g/L, calcium 0.19g/L, magnesium 0.00038g/L.
Embodiment 9
The molybdenum calcining washing waste water pH value of the present embodiment is 3～4, and in waste water, each ionic concn is: molybdenum 24.29g/L, copper 0.5g/L, iron 0.74g/L, potassium 0.8g/L, sodium 0.028g/L, calcium 0.21g/L, magnesium 0.35g/L; The heavy crystalline mother solution pH value of acid is 5, and each indicator ion is: molybdenum 15.74g/L, copper 0.004g/L, iron 0.0026g/L, potassium 0.076g/L, sodium 0.17g/L, calcium 0.015g/L, magnesium 0.024g/L; In calcining molybdenum concentrate, the mass content of molybdenum is 63.03%, and the mass content of copper is 0.13%, and the mass content of the insoluble molybdenum of ammonia is 0.74%.
The method that the molybdenum calcining washing waste water of the present embodiment is processed recycling is:
Stir after molybdenum calcining washing waste water, the heavy crystalline mother solution of acid and calcining molybdenum concentrate are mixed and obtain slurry, the pH value of regulating slurry with nitric acid (also available other acid substitutions) is 2.5, then under temperature is the condition of 100 ℃, slurry is stirred 2h and carries out cleanup acid treatment; Adopt plate-and-frame filter press to carry out solid-liquid separation to the slurry after cleanup acid treatment, the filter cake that separation is obtained is sent into and is carried out conventional ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, and the filtrate that separation is obtained is sent into and processed rear discharging up to standard in Waste Water Treatment; The volume ratio of the heavy crystalline mother solution of the acid in described molybdenum calcining washing waste water and production of molybdic ammonium process is 1: 2.5, and the liquid-solid ratio of described slurry is 5: 1.
The present embodiment is separated the filtrate and the filter cake that obtain detect, the chemical index of filter cake (wt%) is: molybdenum 62.9%, copper 0.010%, iron 1.20%, potassium 0.032%, sodium 0.005%, calcium 0.11%, magnesium 0.0092%; The pH value of filtrate is 2.0, and in filtrate, each ionic concn is: molybdenum 0.18g/L, copper 0.60g/L, iron 0.00014g/L, potassium 0.67g/L, sodium 0.088g/L, calcium 0.00021g/L, magnesium 0.00038g/L.
The above; it is only preferred embodiment of the present invention; be not that the present invention is done any restriction, every any simple modification, change and equivalent structure of above embodiment being done according to the invention technical spirit changes, and all still belongs in the protection domain of technical solution of the present invention.
Claims (8)
1. a molybdenum calcining washing waste water is processed the method for recycling, it is characterized in that, the method is that molybdenum calcining washing waste water is mixed by 1: 0.5～5 volume ratio with the heavy crystalline mother solution of the acid in the production of molybdic ammonium process, make molybdenum in molybdenum calcining washing waste water and the molybdenum in the heavy crystalline mother solution of acid form precipitation and recycle, detailed process comprises the following steps:
Step 1, stir after the heavy crystalline mother solution of the acid in molybdenum calcining washing waste water and production of molybdic ammonium process is mixed by 1: 0.5～5 volume ratio, then regulating the pH value is 1.0～4.0, and continuation stirring 10min～60min obtains solidliquid mixture;
Step 2, solidliquid mixture described in step 1 is carried out solid-liquid separation, the filter cake that separation is obtained is sent into and is carried out ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, the filtrate that separation is obtained is sent into the molybdenum calcining pickling process of production of molybdic ammonium technique and is recycled, and realizes the recycling of Recycle of molybdenum and waste water in molybdenum calcining washing waste water.
2. molybdenum calcining washing waste water according to claim 1 is processed the method for recycling, it is characterized in that, the equipment that solid-liquid separation described in step 2 adopts is plate-and-frame filter press.
3. molybdenum calcining washing waste water according to claim 1 is processed the method for recycling, it is characterized in that, described in step 2 in filtrate molybdenum content be not more than 1.5g/L.
4. molybdenum calcining washing waste water according to claim 1 is processed the method for recycling, it is characterized in that, it is 70 ℃～100 ℃ that filtrate described in step 2 enters the temperature of carrying out cleanup acid treatment in molybdenum calcining pickling process, the pH value is 0.5～2.5, liquid-solid ratio is 2～5: 1, and the cleanup acid treatment time is 1h～3h.
5. molybdenum calcining washing waste water according to claim 4 is processed the method for recycling, it is characterized in that, the method also comprises carries out solid-liquid separation to the slurry after cleanup acid treatment, the filter cake that separation is obtained is sent into and is carried out ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, and the filtrate that separation is obtained is sent into and processed rear discharging up to standard in Waste Water Treatment.
6. a molybdenum calcining washing waste water is processed the method for recycling, it is characterized in that, the method is: obtain slurry with stirring after the heavy crystalline mother solution of the acid in molybdenum calcining washing waste water, production of molybdic ammonium process and calcining molybdenum concentrate mixing, the pH value of regulating slurry is 0.5～2.5, then under temperature is the condition of 70 ℃～100 ℃, slurry is stirred 1h～3h and carries out cleanup acid treatment; Slurry after cleanup acid treatment is carried out solid-liquid separation, and the filter cake that separation is obtained is sent into and is carried out ammonia in the Ammonia leaching of production of molybdic ammonium technique and soak processing, and the filtrate that separation is obtained is sent into and processed rear discharging up to standard in Waste Water Treatment; The volume ratio of the heavy crystalline mother solution of the acid in described molybdenum calcining washing waste water and production of molybdic ammonium process is 1: 0.5～5, and the liquid-solid ratio of described slurry is 2～5: 1.
7. molybdenum calcining washing waste water according to claim 6 is processed the method for recycling, it is characterized in that, in described filtrate, molybdenum content is not more than 0.5g/L.
8. molybdenum calcining washing waste water according to claim 6 is processed the method for recycling, it is characterized in that, the equipment that described solid-liquid separation adopts is plate-and-frame filter press.
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| CN2011104562292A CN102557212B (en) | 2011-12-30 | 2011-12-30 | Method for treating and recycling molybdenum calcine water-washing waste water |
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| CN102978388B (en) * | 2012-11-30 | 2015-02-04 | 成都易态科技有限公司 | Ammonia leaching pretreatment process of molybdenum concentrate or molybdenic acid filter cake |
| CN103553132B (en) * | 2013-10-19 | 2015-06-10 | 金堆城钼业股份有限公司 | Method for preparing ammonium tetramolybdate by treating molybdenum-rich wastewater and waste slag |
| CN104445410A (en) * | 2014-11-14 | 2015-03-25 | 金堆城钼业股份有限公司 | Method for washing commercial molybdenum oxide |
| CN104388681A (en) * | 2014-11-14 | 2015-03-04 | 金堆城钼业股份有限公司 | Treatment method for recycling high-concentration molybdenum calcine washing wastewater |
| CN105177319B (en) * | 2015-08-28 | 2017-05-03 | 金堆城钼业股份有限公司 | Molybdenum disulfide dissolving method |
| CN108128958B (en) * | 2017-12-29 | 2021-01-26 | 金堆城钼业股份有限公司 | Production process for treating ammonia nitrogen wastewater |
| CN109534533A (en) * | 2018-11-06 | 2019-03-29 | 金堆城钼业股份有限公司 | A kind of administering method of molybdenum calcining pickling waste waters |
| CN115747529B (en) * | 2022-10-28 | 2023-12-15 | 中南大学 | Molybdenum calcine treatment method |
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Non-Patent Citations (2)
| Title |
|---|
| 桂林等.钼酸铵生产中的废水处理.《中国钼业》.1999,第23卷(第5期), |
| 钼酸铵生产中的废水处理;桂林等;《中国钼业》;199910;第23卷(第5期);25－26 * |
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