CN103553132A - Method for preparing ammonium tetramolybdate by treating molybdenum-rich wastewater and waste slag - Google Patents
Method for preparing ammonium tetramolybdate by treating molybdenum-rich wastewater and waste slag Download PDFInfo
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Abstract
The invention discloses a method for preparing ammonium tetramolybdate by treating molybdenum-rich wastewater and waste slag, which comprises the following steps: 1. washing a molybdenum roasted product with water, concentrating wastewater, and uniformly mixing with an acid precipitation crystal mother solution in an ammonium molybdate production process, thereby obtaining a mixed solution; 2. adding a molybdenum roasted product into water-washed molybdenum roasted product ammonia leaching waste slag, adding into the mixed solution, regulating the pH value, magnetizing, and stirring to react to obtain a solid-liquid mixed slurry; 3. carrying out solid-liquid separation, and carrying out ammonia leaching on the filter cake; 4. carrying out solid-liquid separation to obtain an ammonia leaching solution and ammonia leaching slag; 5. carrying out ammonia leaching on the ammonia leaching slag; and 6. removing impurities from the ammonia leaching solution, purifying, carrying out acid precipitation, and filtering to obtain the solid ammonium tetramolybdate. The molybdenum roasted product-doped molybdenum roasted product ammonia leaching waste slag is added into the wastewater and acid precipitation mother solution, and liquid-phase magnetization is carried out to efficiently utilize the molybdenum resources in the wastewater and waste slag, thereby greatly lowering the treatment cost for molybdenum-containing waste slag and wastewater, being energy-saving and environment-friendly, and effectively enhancing the molybdenum resource utilization ratio in molybdenum roasted product water-washing concentrated wastewater and ammonia leaching waste slag.
Description
Technical field
The invention belongs to molybdenum resource recycling technical field, be specifically related to a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing.
Background technology
Tradition is prepared and in production of molybdic ammonium, is adopted that pickling molybdenum calcining, ammonia soak, acid is sunk, ammonia is molten, evaporative crystallization is prepared into ammonium dimolybdate, in this art production process in pickling with acid is heavy can produce a large amount of acid ammonia nitrogen waste waters, serious environment pollution.
Washing molybdenum calcining is produced ammonium dimolybdate technique, owing to effectively evading the drawback of the contaminate environment of traditional technology generation ammonia nitrogen waste water.Become the world and praise highly one of main flow technique of environmental protection production ammonium dimolybdate technique, but find in this process implementing process, the waste water that washing molybdenum calcining produces is higher containing molybdenum amount, on average can reach 10g/L～30g/L left and right, and pH value is in 3～4 left and right.Add the existing calcining molybdenum concentrate quality level of China generally lower, the waste residue after ammonia soaks is containing molybdenum amount up to more than 20%～30%, and it is very low that washing molybdenum calcining is produced ammonium dimolybdate molybdenum turnover ratio, had a strong impact on the further promotion and application of this technique.
Because adopting existing technique pickling molybdenum calcining mostly, China except heteroacid is heavy, produces ammonium tetramolybdate technique.Therefore it is imperative that the heavy crystalline mother solution of waste water, waste residue and acid that waste water, waste residue and pickling molybdenum calcining washing molybdenum calcining being produced produces carries out comprehensive treating process.For the traditional method of the recovery of molybdenum in waste liquid, be ion-exchange and extraction process at present, but all there is environmental protection and long processing period in these two kinds of methods, the problems such as regeneration difficulty.In CN102557212 patent, introduced a kind of method that reclaims molybdenum, the method is 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, to stir and to obtain slurry, regulating the pH value of slurry is 0.5～2.5, then under temperature is the condition of 70 ℃～100 ℃, slurry is stirred to 1h～3h and carries out cleanup acid treatment; Slurry after cleanup acid treatment is carried out to solid-liquid separation, and the filter cake that separation is obtained is sent into and in the Ammonia leaching of production of molybdic ammonium technique, is carried out ammonia and soak processing, and the filtrate that separation is obtained is sent into and in Waste Water Treatment, processed rear discharge up to standard.Although the method also can reclaim molybdenum preferably from washing waste water, but this technique removal of impurities ability, only have to process containing molybdenum amount and be greater than 61% or the grade calcining molybdenum concentrate of Gao Gengchun more, could meet the requirement of final ammonium molybdate quality product, for production of molybdic ammonium technique, its Technological adaptability is poor in a word preferably.
For ammonia, soaking waste residue molybdenum recovery traditional method is after oxygen-enriched air roasting method or high pressure base cooking method are processed, then does ammonium molybdate and Sodium orthomolybdate.As high pressure alkaline leaching, technical process is:
A ammonia is washed: higher-grade ammonia leaching residue is washed with ammoniacal liquor, guarantee that molybdenum stable content in ammonia washery slag is in 18.5% left and right;
B ammonia soaks: ammonia washery slag soaks slag molybdenum content and is reduced to 10.85% left and right from 18.5% left and right after an ammonia soaks, and the average leaching yield of molybdenum is 47.65%;
C alkali soaks: after one time ammonia soaks soak slag by a certain percentage the alkali after high pressure base is soaked soak slag molybdenum content and by original 10.85%, be reduced to below 2%, the average leaching yield of molybdenum is 87.72%, through ammonia soak, the average leaching yield of alkali total molybdenum of former higher-grade ammonia leaching residue after soaking is 94%;
D filtration, purification: the ammonia leaching solution after ammonia is soaked purifies, and alkali immersion liquid purifies recovery by ion-exchange;
E acid is heavy: by carrying out acid containing molybdenum liquid and sink after purifying, prepare ammonium tetramolybdate;
F drying and packaging: the ammonium tetramolybdate of preparation is carried out to drying and packaging and obtain ammonium tetramolybdate product.
As can be seen from above: this technique subject matter is that operation is long, cost is high, uneconomical.
In addition, in CN101660045 patent, disclosing " leaching the method that reclaims molybdenum from ammonia leaching residue " the method is mainly to sieve by ammonia leaching residue, in its screen overflow, add respectively sodium carbonate and water to stir pulp, be heated to 90～100 ℃ and add clorox, constant temperature stirs, and filters to obtain an alkali immersion liquid of molybdenum; In its screen underflow, add again sodium carbonate and water to stir pulp, the alkali immersion liquid of molybdenum that obtains of step in dropping, 90～100 ℃ of constant temperature, dropwise, and filter to obtain the alkali immersion liquid of molybdenum, then reclaim molybdenum from the alkali immersion liquid of molybdenum.There is complex steps in this technique, and easily to decompose the medicament amount of expending large due to the high clorox of temperature, and the concentration of the alkali immersion liquid molybdenum simultaneously leaching is little, and after removal of impurities, evaporation concentration energy consumption is very large, and application prospect is good.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, and a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing is provided.The molybdenum calcining ammonia that the present invention's employing interpolation in the heavy mother liquor of waste water and acid is mixed with molybdenum calcining soaks waste residue, by liquid phase, magnetizes processing, and the molybdenum resource of waste water, waste residue is efficiently utilized, and makes filtrate return to the rear meet the requirement of environmental protection of conventional Waste Water Treatment processing simultaneously.Compare with washing waste water individual curing technique with ammonia leaching residue, the present invention is directly used for production of molybdic ammonium by ammonia leaching residue and the concentrated waste water of washing, molybdenum-containing waste slag, cost for wastewater treatment have greatly been reduced, not only energy-saving and environmental protection, and effectively improved the concentrated waste water of molybdenum calcining washing and ammonia soaks waste residue molybdenum resource utilization, the features such as have facility investment not high, technique is efficient, practical.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind ofly process the method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate, it is characterized in that, the method comprises the following steps:
Step 1, molybdenum calcining washing waste water is concentrated into molybdenum content is not less than 90g/L, then the molybdenum calcining washing waste water after concentrated is sunk to crystalline mother solution by 1 with the acid in production of molybdic ammonium process: the volume ratio of (0.5～2) mixes, and obtains mixed solution;
Step 2, to washing molybdenum calcining ammonia, soak and in waste residue, add molybdenum calcining, then the washing molybdenum calcining ammonia that is added with molybdenum calcining being soaked to waste residue under agitation condition adds described in step 1 in mixed solution, obtain solidliquid mixture, the pH value that regulates described solidliquid mixture is 0.5～1.5, again to regulating the solidliquid mixture after pH value to magnetize processing, solidliquid mixture stirring reaction 30min～90min at 50 ℃～70 ℃ after finally magnetization being processed, obtains solid-liquid mixed slurry; The addition of described molybdenum calcining soaks 60%～80% of waste residue and molybdenum calcining total mass for washing molybdenum calcining ammonia; The liquid-solid ratio of described solidliquid mixture is (2～5): 1;
Step 3, the mixed slurry of solid-liquid described in step 2 is carried out to solid-liquid separation, the filter cake that separation is obtained is sent into and in the Ammonia leaching of production of molybdic ammonium technique, is carried out ammonia and soak processing;
Step 4, the material that ammonia in step 3 is soaked after processing carry out solid-liquid separation, obtain ammonia leaching solution and ammonia leaching residue;
Step 5, ammonia leaching residue described in step 4 is sent into and in the Ammonia leaching of production of molybdic ammonium technique, carried out ammonia and soak processing, the material then ammonia being soaked after processing carries out solid-liquid separation, and the filtrate that separation is obtained is returned described in step 3 in Ammonia leaching;
Step 6, adopt ion-exchange to carry out removal of impurities to ammonia leaching solution described in step 4, the ammonia leaching solution after then adopting electric drive membrane separation apparatus to removal of impurities purifies, and the ammonia leaching solution acid after purifying is heavy, obtains solid ammonium tetramolybdate after filtration.
A kind of above-mentioned method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing, in step 2, adding the quality percentage composition that washing molybdenum calcining ammonia before molybdenum calcining soaks molybdenum in waste residue is 15%～30%.
A kind of above-mentioned method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing, the magneticstrength that described in step 2, magnetization is processed is not less than 25 kilogausss, and the magnetization treatment time is 10min～30min.
A kind of above-mentioned method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing, the equipment that solid-liquid separation described in step 3 adopts is frame vacuum filtration machine.
A kind of above-mentioned method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing, the temperature that ammonia described in step 3 soaks processing is 60 ℃～70 ℃, and pH value is 8.5～9.5, and liquid-solid ratio is (2～5): 1, the treatment time is 1h～3h.
A kind of above-mentioned method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing, described in step 3, in filter cake, the insoluble molybdenum quality of ammonia percentage composition is not more than 2.0%.
A kind of above-mentioned method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing, the equipment that solid-liquid separation described in step 4 adopts is wind pressure type paper blotter press.
The above-mentioned a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate, diaphragm filter press that the equipment that solid-liquid separation described in step 5 adopts washs for band processed.
A kind of above-mentioned method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing, the ion exchange resin that ion-exchange described in step 6 adopts is macropore chelating Zeo-karb.
The present invention compared with prior art has the following advantages:
1, the present invention adopts and in waste water and the heavy mother liquor of acid, to add the molybdenum calcining ammonia that is mixed with molybdenum calcining and soak waste residue, by liquid phase, magnetize processing, the molybdenum resource of waste water, waste residue is efficiently utilized, made filtrate return to conventional Waste Water Treatment simultaneously and process rear meet the requirement of environmental protection.
2, compare with washing waste water individual curing technique with ammonia leaching residue, the present invention is directly used for production of molybdic ammonium by ammonia leaching residue and the concentrated waste water of washing, molybdenum-containing waste slag, cost for wastewater treatment have greatly been reduced, not only energy-saving and environmental protection, and effectively improved the concentrated waste water of molybdenum calcining washing and ammonia soaks waste residue molybdenum resource utilization, the features such as have facility investment not high, technique is efficient, practical.
3, the present invention prepares in ammonium molybdate process at waste water and dregs magnetization impurity elimination technology and the electricity membrane separation for removing impurities technology of tending to act of using first, make potassium content in product be less than 10ppm, quality has reached international most advanced level, promoted the transformation from extensive, scalar type to meticulous type, mass type of domestic production of molybdic ammonium waste residue, waste water reclamation molybdenum technology and technique, improved the rich molybdenum waste water of China, waste residue molybdenum resource comprehensive recycling level, indicated that rich molybdenum waste water, waste residue recycling have gone up a brand-new step.
4, the rich molybdenum washing waste water producing in energy system solution molybdenum in China acid ammonium production process of the present invention and the recovery and reuse problem of ammonia leaching residue molybdenum.Reduce pilot process and occupy because of the metal that waste water, waste residue produce, eliminate in production of molybdic ammonium line waste water treatment process, produce containing molybdenum waste material and ammonia leaching residue warehousing pressure, significant to improving turnover ratio and the molybdenum resource utilization of molybdenum.
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment
Embodiment 1
Step 1, molybdenum calcining washing waste water is concentrated, in the waste water after concentrating, major metal ionic concn is: Mo93.54g/L, Cu0.12g/L, Fe3.29mg/L, K0.27g/L, Na0.18g/L, Ca0.91mg/L, Mg3.50mg/L; Then the crystalline mother solution that the molybdenum calcining washing waste water after concentrated and the acid in production of molybdic ammonium process sunk mixes by the volume ratio of 1: 1, obtain mixed solution, in the heavy mother liquor of acid, major metal ionic concn is: Mo6.06g/L, Cu0.006g/L, Fe1.09mg/L, K0.074g/L, Na0.17g/L, Ca0.021g/L, Mg0.04mg/L;
Step 2, the washing molybdenum calcining ammonia that is 21.7% to the quality percentage composition of Mo soak in waste residue and add molybdenum calcining, and in molybdenum calcining, major metal mass content is: Mo63.38%, Cu0.09%, Fe1.18%, K0.07%, Na0.018%, Ca0.25%; Then the washing molybdenum calcining ammonia that is added with molybdenum calcining being soaked to waste residue under agitation condition adds described in step 1 in mixed solution, obtain solidliquid mixture, the pH value that regulates described solidliquid mixture is 0.5, again to regulating the solidliquid mixture after pH value to magnetize processing, solidliquid mixture stirring reaction 30min at 50 ℃ after finally magnetization being processed, obtains solid-liquid mixed slurry; The addition of described molybdenum calcining soaks 70% of waste residue and molybdenum calcining total mass for washing molybdenum calcining ammonia; The liquid-solid ratio of described solidliquid mixture (mass ratio) is 3: 1; The magneticstrength that described magnetization is processed is not less than 25 kilogausss, and the magnetization treatment time is 10min;
Step 3, employing frame vacuum filtration machine carry out solid-liquid separation to the mixed slurry of solid-liquid described in step 2, the filter cake that separation is obtained and filtrate respectively sample presentation are detected, the major metal mass content that filter cake detects after drying is: Mo44.24%, Cu0.068%, Fe4.73%, K0.087%, Na0.063%, Ca0.67%, Mg0.092%, in filter cake, the quality percentage composition of the insoluble molybdenum of ammonia is 1.7%; The pH value of filtrate is 0.5, and in filtrate, major metal ionic concn is: Mo0.60g/L, Cu0.92g/L, Fe0.14mg/L, K0.30g/L, Na0.18g/L, Ca0.61g/L, Mg1.49mg/L; The filter cake that separation is obtained is sent into and in the Ammonia leaching of production of molybdic ammonium technique, is carried out ammonia and soak processing, and the temperature that ammonia soaks processing is 65 ℃, and pH value is 8.5～9.0, and liquid-solid ratio (mass ratio) is 3: 1, and the treatment time is 1.5h; Filtrate is sent in Waste Water Treatment and processed rear discharge up to standard, realize the recycling of the concentrated waste water of molybdenum calcining washing and ammonia leaching residue molybdenum;
Step 4, the material that adopts wind pressure type paper blotter press to soak after processing ammonia in step 3 carry out solid-liquid separation, obtain ammonia leaching solution and ammonia leaching residue, after testing, in ammonia leaching solution, major metal ionic concn is: Mo150.48g/L, Cu0.19g/L, Fe5.33mg/L, K0.19g/L, Na0.089g/L, Ca4.88mg/L, Mg16.71mg/L, in ammonia leaching residue, the quality percentage composition of Mo is 19.10%, the quality percentage composition of the insoluble molybdenum of ammonia is 1.60%;
Step 5, ammonia leaching residue described in step 4 is sent into and in the Ammonia leaching of production of molybdic ammonium technique, carried out ammonia and soak processing, then the material that the diaphragm filter press that adopts band to wash soaks after processing ammonia carries out solid-liquid separation, the filtrate that separation is obtained is returned described in step 3 in Ammonia leaching, the filter residue that separation is obtained is sent into slag field and is focused on, after testing, in filter residue, the quality percentage composition of Mo is 6.2%, and the quality percentage composition of the insoluble molybdenum of ammonia is 1.5%;
Step 6, employing TP207 duplicate removal metal macropore chelating sun resin carry out removal of impurities to ammonia leaching solution described in step 4, remove the beavy metal impurities such as copper, calcium, magnesium, ammonia leaching solution sampling after removal of impurities is detected, its major metal ionic concn is: Mo150.07g/L, Cu0.003g/L, Fe5.0mg/L, K0.192g/L, Na0.092g/L, Ca3.01mg/L, Mg1.51mg/L; Then adopt electric drive membrane separation apparatus, utilizing electromotive force to order about alkali metal cation in ammonia leaching solution crosses the ammonia leaching solution of diaphragm after to removal of impurities and purifies, ammonia leaching solution sampling after purifying is detected, its major metal ionic concn is Mo150.07g/L, Cu2.9mg/L, Fe4.50mg/L, K0.020g/L, Na0.012g/L, Ca3.0mg/L, Mg1.5mg/L; After ammonia leaching solution acid after purifying is heavy, filter, to filtering the filtrate and the ammonium tetramolybdate filter cake that obtain, sample respectively detection, in ammonium tetramolybdate filter cake, metal quality content is Mo59.20%, Cu0.0001%, Fe0.0002%, K0.0007%, Na0.0003%, Ca0.0002%, Mg0.0002%, moisture 4%, in filtrate, major metal ionic concn is Mo7.12g/L, Cu0.5mg/L, Fe1.03mg/L, K0.024g/L, Na0.016g/L, Ca0.002g/L, Mg0.06mg/L.
The molybdenum calcining ammonia that the present embodiment employing interpolation in waste water and the heavy mother liquor of acid is mixed with molybdenum calcining soaks waste residue, by liquid phase, magnetize processing, make waste water, the molybdenum resource of waste residue is efficiently utilized, make filtrate return to conventional Waste Water Treatment simultaneously and process rear meet the requirement of environmental protection, compare with washing waste water individual curing technique with ammonia leaching residue, the present embodiment is directly used for production of molybdic ammonium by ammonia leaching residue and the concentrated waste water of washing, greatly reduced molybdenum-containing waste slag, cost for wastewater treatment, not only energy-conservation, environmental protection, and effectively improved the concentrated waste water of molybdenum calcining washing and ammonia soaks waste residue molybdenum resource utilization, there is facility investment not high, technique is efficient, the features such as practicality.
Comparative example 1
Adopt ammonia leaching solution described in embodiment 1 step 4 directly to carry out acid heavy, after filtration, filtrate and ammonium tetramolybdate filter cake are sampled respectively to detection, in ammonium tetramolybdate filter cake, metal quality content is Mo58.15%, Cu0.0016%, Fe0.0007%, K0.0144%, Na0.0010%, Ca0.0025%, Mg0.0010%, in filtrate, major metal ionic concn is Mo18.30g/L, Cu0.096g/L, Fe1.53mg/L, K0.12g/L, Na0.063g/L, Ca0.02141g/L, Mg0.076g/L.
Embodiment 2
Step 1, molybdenum calcining washing waste water is concentrated, in the waste water after concentrating, major metal ionic concn is: Mo90g/L, Cu0.13g/L, Fe3.28mg/L, K0.27g/L, Na0.15g/L, Ca0.90mg/L, Mg3.50mg/L; Then the crystalline mother solution that the molybdenum calcining washing waste water after concentrated and the acid in production of molybdic ammonium process sunk mixes by the volume ratio of 1: 0.5, obtain mixed solution, in the heavy mother liquor of acid, major metal ionic concn is: Mo6.06g/L, Cu0.006g/L, Fe1.09mg/L, K0.074g/L, Na0.17g/L, Ca0.021g/L, Mg0.04mg/L;
Step 2, the washing molybdenum calcining ammonia that is 30% to the quality percentage composition of Mo soak in waste residue and add molybdenum calcining, and in molybdenum calcining, major metal mass content is: Mo63.35%, Cu0.088%, Fe1.15%, K0.08%, Na0.018%, Ca0.275%; Then the washing molybdenum calcining ammonia that is added with molybdenum calcining being soaked to waste residue under agitation condition adds described in step 1 in mixed solution, obtain solidliquid mixture, the pH value that regulates described solidliquid mixture is 1.5, again to regulating the solidliquid mixture after pH value to magnetize processing, solidliquid mixture stirring reaction 60min at 70 ℃ after finally magnetization being processed, obtains solid-liquid mixed slurry; The addition of described molybdenum calcining soaks 60% of waste residue and molybdenum calcining total mass for washing molybdenum calcining ammonia; The liquid-solid ratio of described solidliquid mixture (mass ratio) is 2: 1; The magneticstrength that described magnetization is processed is 30 kilogausss, and the magnetization treatment time is 30min;
Step 3, employing frame vacuum filtration machine carry out solid-liquid separation to the mixed slurry of solid-liquid described in step 2, the filter cake that separation is obtained and filtrate respectively sample presentation are detected, the major metal mass content that filter cake detects after drying is: Mo44.1%, Cu0.065%, Fe4.65%, K0.09%, Na0.062%, Ca0.7%, Mg0.091%, in filter cake, the quality percentage composition of the insoluble molybdenum of ammonia is 2.0%; The pH value of filtrate is 0.5, and in filtrate, major metal ionic concn is: Mo0.61g/L, Cu0.95g/L, Fe0.135mg/L, K0.31g/L, Na0.18g/L, Ca0.602g/L, Mg1.48mg/L; The filter cake that separation is obtained is sent into and in the Ammonia leaching of production of molybdic ammonium technique, is carried out ammonia and soak processing, and the temperature that ammonia soaks processing is 60 ℃, and pH value is 9.0～9.5, and liquid-solid ratio (mass ratio) is 2: 1, and the treatment time is 3h; Filtrate is sent in Waste Water Treatment and processed rear discharge up to standard, realize the recycling of the concentrated waste water of molybdenum calcining washing and ammonia leaching residue molybdenum;
Step 4, the material that adopts wind pressure type paper blotter press to soak after processing ammonia in step 3 carry out solid-liquid separation, obtain ammonia leaching solution and ammonia leaching residue, after testing, in ammonia leaching solution, major metal ionic concn is: Mo153.5g/L, Cu0.175g/L, Fe5.3mg/L, K0.19g/L, Na0.08g/L, Ca4.85mg/L, Mg16.65mg/L, in ammonia leaching residue, the quality percentage composition of Mo is 18.1%, the quality percentage composition of the insoluble molybdenum of ammonia is 1.90%;
Step 5, ammonia leaching residue described in step 4 is sent into and in the Ammonia leaching of production of molybdic ammonium technique, carried out ammonia and soak processing, then the material that the diaphragm filter press that adopts band to wash soaks after processing ammonia carries out solid-liquid separation, the filtrate that separation is obtained is returned described in step 3 in Ammonia leaching, the filter residue that separation is obtained is sent into slag field and is focused on, after testing, in filter residue, the quality percentage composition of Mo is 4.1%, and the quality percentage composition of the insoluble molybdenum of ammonia is 2.3%;
Step 6, employing TP207 duplicate removal metal macropore chelating sun resin carry out removal of impurities to ammonia leaching solution described in step 4, remove the beavy metal impurities such as copper, calcium, magnesium, ammonia leaching solution sampling after removal of impurities is detected, its major metal ionic concn is: Mo152.28g/L, Cu2.8mg/L, Fe4.0mg/L, K0.19g/L, Na0.092g/L, Ca3.05mg/L, Mg1.45mg/L; Then adopt electric drive membrane separation apparatus, utilizing electromotive force to order about alkali metal cation in ammonia leaching solution crosses the ammonia leaching solution of diaphragm after to removal of impurities and purifies, ammonia leaching solution sampling after purifying is detected, its major metal ionic concn is Mo152.28g/L, Cu2.6mg/L, Fe3.40mg/L, K0.018g/L, Na0.01g/L, Ca2.5mg/L, Mg1.42mg/L; After ammonia leaching solution acid after purifying is heavy, filter, to filtering the filtrate and the ammonium tetramolybdate filter cake that obtain, sample respectively detection, in ammonium tetramolybdate filter cake, metal quality content is Mo59.75%, Cu0.00009%, Fe0.00018%, K0.00067%, Na0.0003%, Ca0.00017%, Mg0.0002%, moisture 5.3%, in filtrate, major metal ionic concn is Mo7.01g/L, Cu0.5mg/L, Fe1.12mg/L, K0.02g/L, Na0.016g/L, Ca0.0022g/L, Mg0.057mg/L.
The molybdenum calcining ammonia that the present embodiment employing interpolation in waste water and the heavy mother liquor of acid is mixed with molybdenum calcining soaks waste residue, by liquid phase, magnetize processing, make waste water, the molybdenum resource of waste residue is efficiently utilized, make filtrate return to conventional Waste Water Treatment simultaneously and process rear meet the requirement of environmental protection, compare with washing waste water individual curing technique with ammonia leaching residue, the present embodiment is directly used for production of molybdic ammonium by ammonia leaching residue and the concentrated waste water of washing, greatly reduced molybdenum-containing waste slag, cost for wastewater treatment, not only energy-conservation, environmental protection, and effectively improved the concentrated waste water of molybdenum calcining washing and ammonia soaks waste residue molybdenum resource utilization, there is facility investment not high, technique is efficient, the features such as practicality.
Comparative example 2
Adopt ammonia leaching solution described in embodiment 2 step 4 directly to carry out acid heavy, after filtration, filtrate and ammonium tetramolybdate filter cake are sampled respectively to detection, in ammonium tetramolybdate filter cake, metal quality content is Mo58.25%, Cu0.0014%, Fe0.0008%, K0.0170%, Na0.0013%, Ca0.0012%, Mg0.0008%, in filtrate, major metal ionic concn is Mo17.00g/L, Cu0.12g/L, Fe1.98mg/L, K0.15g/L, Na0.079g/L, Ca0.03018g/L, Mg0.0521g/L.
Embodiment 3
Step 1, molybdenum calcining washing waste water is concentrated, in the waste water after concentrating, major metal ionic concn is: Mo95g/L, Cu0.15g/L, Fe3.32mg/L, K0.29g/L, Na0.15g/L, Ca0.88mg/L, Mg3.42mg/L; Then the crystalline mother solution that the molybdenum calcining washing waste water after concentrated and the acid in production of molybdic ammonium process sunk mixes by the volume ratio of 1: 2, obtain mixed solution, in the heavy mother liquor of acid, major metal ionic concn is: Mo6.06g/L, Cu0.006g/L, Fe1.09mg/L, K0.074g/L, Na0.17g/L, Ca0.021g/L, Mg0.04mg/L;
Step 2, the washing molybdenum calcining ammonia that is 15% to the quality percentage composition of Mo soak in waste residue and add molybdenum calcining, and in molybdenum calcining, major metal mass content is: Mo63.38%, Cu0.09%, Fe1.18%, K0.07%, Na0.018%, Ca0.25%; Then the washing molybdenum calcining ammonia that is added with molybdenum calcining being soaked to waste residue under agitation condition adds described in step 1 in mixed solution, obtain solidliquid mixture, the pH value that regulates described solidliquid mixture is 1.0, again to regulating the solidliquid mixture after pH value to magnetize processing, solidliquid mixture stirring reaction 90min at 60 ℃ after finally magnetization being processed, obtains solid-liquid mixed slurry; The addition of described molybdenum calcining soaks 80% of waste residue and molybdenum calcining total mass for washing molybdenum calcining ammonia; The liquid-solid ratio of described solidliquid mixture (mass ratio) is 5: 1; The magneticstrength that described magnetization is processed is 35 kilogausss, and the magnetization treatment time is 20min;
Step 3, employing frame vacuum filtration machine carry out solid-liquid separation to the mixed slurry of solid-liquid described in step 2, the filter cake that separation is obtained and filtrate respectively sample presentation are detected, the major metal mass content that filter cake detects after drying is: Mo44.45%, Cu0.07%, Fe4.72%, K0.088%, Na0.062%, Ca0.68%, Mg0.089%, in filter cake, the quality percentage composition of the insoluble molybdenum of ammonia is 1.9%; The pH value of filtrate is 0.5, and in filtrate, major metal ionic concn is: Mo0.61g/L, Cu0.92g/L, Fe0.15mg/L, K0.32g/L, Na0.16g/L, Ca0.60g/L, Mg1.45mg/L; The filter cake that separation is obtained is sent into and in the Ammonia leaching of production of molybdic ammonium technique, is carried out ammonia and soak processing, and the temperature that ammonia soaks processing is 70 ℃, and pH value is 8.5～9.0, and liquid-solid ratio (mass ratio) is 5: 1, and the treatment time is 1h; Filtrate is sent in Waste Water Treatment and processed rear discharge up to standard, realize the recycling of the concentrated waste water of molybdenum calcining washing and ammonia leaching residue molybdenum;
Step 4, the material that adopts wind pressure type paper blotter press to soak after processing ammonia in step 3 carry out solid-liquid separation, obtain ammonia leaching solution and ammonia leaching residue, after testing, in ammonia leaching solution, major metal ionic concn is: Mo151.0g/L, Cu0.2g/L, Fe5.35mg/L, K0.19g/L, Na0.087g/L, Ca4.85mg/L, Mg16.62mg/L, in ammonia leaching residue, the quality percentage composition of Mo is 21.1%, the quality percentage composition of the insoluble molybdenum of ammonia is 1.70%;
Step 5, ammonia leaching residue described in step 4 is sent into and in the Ammonia leaching of production of molybdic ammonium technique, carried out ammonia and soak processing, then the material that the diaphragm filter press that adopts band to wash soaks after processing ammonia carries out solid-liquid separation, the filtrate that separation is obtained is returned described in step 3 in Ammonia leaching, the filter residue that separation is obtained is sent into slag field and is focused on, after testing, in filter residue, the quality percentage composition of Mo is 5.5%, and the quality percentage composition of the insoluble molybdenum of ammonia is 2.2%;
Step 6, employing TP207 duplicate removal metal macropore chelating sun resin carry out removal of impurities to ammonia leaching solution described in step 4, remove the beavy metal impurities such as copper, calcium, magnesium, ammonia leaching solution sampling after removal of impurities is detected, its major metal ionic concn is: Mo150.75g/L, Cu3.2mg/L, Fe5.1mg/L, K0.190g/L, Na0.092g/L, Ca3.03mg/L, Mg1.45mg/L; Then adopt electric drive membrane separation apparatus, utilizing electromotive force to order about alkali metal cation in ammonia leaching solution crosses the ammonia leaching solution of diaphragm after to removal of impurities and purifies, ammonia leaching solution sampling after purifying is detected, its major metal ionic concn is Mo150.75g/L, Cu3.0mg/L, Fe4.64mg/L, K0.018g/L, Na0.012g/L, Ca2.9mg/L, Mg1.41mg/L; After ammonia leaching solution acid after purifying is heavy, filter, to filtering the filtrate and the ammonium tetramolybdate filter cake that obtain, sample respectively detection, in ammonium tetramolybdate filter cake, metal quality content is Mo59.84%, Cu0.0001%, Fe0.0002%, K0.0006%, Na0.0005%, Ca0.0002%, Mg0.0002%, moisture 4.5%, in filtrate, major metal ionic concn is Mo7.35g/L, Cu0.7mg/L, Fe1.05mg/L, K0.02g/L, Na0.018g/L, Ca0.002g/L, Mg0.057mg/L.
The molybdenum calcining ammonia that the present embodiment employing interpolation in waste water and the heavy mother liquor of acid is mixed with molybdenum calcining soaks waste residue, by liquid phase, magnetize processing, make waste water, the molybdenum resource of waste residue is efficiently utilized, make filtrate return to conventional Waste Water Treatment simultaneously and process rear meet the requirement of environmental protection, compare with washing waste water individual curing technique with ammonia leaching residue, the present embodiment is directly used for production of molybdic ammonium by ammonia leaching residue and the concentrated waste water of washing, greatly reduced molybdenum-containing waste slag, cost for wastewater treatment, not only energy-conservation, environmental protection, and effectively improved the concentrated waste water of molybdenum calcining washing and ammonia soaks waste residue molybdenum resource utilization, there is facility investment not high, technique is efficient, the features such as practicality.
Comparative example 3
Adopt ammonia leaching solution described in embodiment 3 step 4 directly to carry out acid heavy, after filtration, filtrate and ammonium tetramolybdate filter cake are sampled respectively to detection, in ammonium tetramolybdate filter cake, metal quality content is Mo59.17%, Cu0.0011%, Fe0.0006%, K0.0154%, Na0.0012%, Ca0.0023%, Mg0.0009%, in filtrate, major metal ionic concn is Mo15.42g/L, Cu0.039g/L, Fe2.01mg/L, K0.169g/L, Na0.042g/L, Ca0.03318g/L, Mg0.0612g/L.
From embodiment 1 and comparative example 1, embodiment 2 and comparative example 2 and embodiment 3 can find out with the data of comparative example 3, the present invention adopts ion-exchange removal of impurities in conjunction with the electricity membrane sepn purification techniques of tending to act, can effectively remove the foreign metal content in product, make potassium content in product be less than 10ppm, quality has reached international most advanced level, promoted domestic production of molybdic ammonium waste residue, waste water reclamation molybdenum technology and technique are from extensive style, scalar type is to meticulous type, the transformation of mass type, improved the rich molybdenum waste water of China, waste residue molybdenum resource comprehensive is recycled level, indicate rich molybdenum waste water, waste residue recycling has gone up a brand-new step.
The above; it is only preferred embodiment of the present invention; not the present invention is done to any restriction, every any simple modification of above embodiment being done according to invention technical spirit, change and equivalent structure change, and all still belong in the protection domain of technical solution of the present invention.
Claims (9)
1. process rich molybdenum waste water waste residue and prepare a method for ammonium tetramolybdate, it is characterized in that, the method comprises the following steps:
Step 1, molybdenum calcining washing waste water is concentrated into molybdenum content is not less than 90g/L, then the molybdenum calcining washing waste water after concentrated is sunk to crystalline mother solution by 1 with the acid in production of molybdic ammonium process: the volume ratio of (0.5～2) mixes, and obtains mixed solution;
Step 2, to washing molybdenum calcining ammonia, soak and in waste residue, add molybdenum calcining, then the washing molybdenum calcining ammonia that is added with molybdenum calcining being soaked to waste residue under agitation condition adds described in step 1 in mixed solution, obtain solidliquid mixture, the pH value that regulates described solidliquid mixture is 0.5～1.5, again to regulating the solidliquid mixture after pH value to magnetize processing, solidliquid mixture stirring reaction 30min～90min at 50 ℃～70 ℃ after finally magnetization being processed, obtains solid-liquid mixed slurry; The addition of described molybdenum calcining soaks 60%～80% of waste residue and molybdenum calcining total mass for washing molybdenum calcining ammonia; The liquid-solid ratio of described solidliquid mixture is (2～5): 1;
Step 3, the mixed slurry of solid-liquid described in step 2 is carried out to solid-liquid separation, the filter cake that separation is obtained is sent into and in the Ammonia leaching of production of molybdic ammonium technique, is carried out ammonia and soak processing;
Step 4, the material that ammonia in step 3 is soaked after processing carry out solid-liquid separation, obtain ammonia leaching solution and ammonia leaching residue;
Step 5, ammonia leaching residue described in step 4 is sent into and in the Ammonia leaching of production of molybdic ammonium technique, carried out ammonia and soak processing, the material then ammonia being soaked after processing carries out solid-liquid separation, and the filtrate that separation is obtained is returned described in step 3 in Ammonia leaching;
Step 6, adopt ion-exchange to carry out removal of impurities to ammonia leaching solution described in step 4, the ammonia leaching solution after then adopting electric drive membrane separation apparatus to removal of impurities purifies, and the ammonia leaching solution acid after purifying is heavy, obtains solid ammonium tetramolybdate after filtration.
2. a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing according to claim 1, is characterized in that, in step 2, adding the quality percentage composition that washing molybdenum calcining ammonia before molybdenum calcining soaks molybdenum in waste residue is 15%～30%.
3. a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing according to claim 1, is characterized in that, the magneticstrength that described in step 2, magnetization is processed is not less than 25 kilogausss, and the magnetization treatment time is 10min～30min.
4. a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing according to claim 1, is characterized in that, the equipment that solid-liquid separation described in step 3 adopts is frame vacuum filtration machine.
5. a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing according to claim 1, it is characterized in that, the temperature that ammonia described in step 3 soaks processing is 60 ℃～70 ℃, and pH value is 8.5～9.5, liquid-solid ratio is (2～5): 1, and the treatment time is 1h～3h.
6. a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing according to claim 1, is characterized in that, described in step 3, in filter cake, the insoluble molybdenum quality of ammonia percentage composition is not more than 2.0%.
7. a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing according to claim 1, is characterized in that, the equipment that solid-liquid separation described in step 4 adopts is wind pressure type paper blotter press.
8. a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing according to claim 1, is characterized in that, the equipment that solid-liquid separation described in step 5 adopts is the diaphragm filter press of band washing.
9. a kind of method that rich molybdenum waste water waste residue is prepared ammonium tetramolybdate of processing according to claim 1, is characterized in that, the ion exchange resin that ion-exchange described in step 6 adopts is macropore chelating Zeo-karb.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109775760A (en) * | 2019-03-11 | 2019-05-21 | 中国有色金属工业西安勘察设计研究院有限公司 | Ultralow potassium ammonium molybdate solution, ammonium molybdate solution derived product and preparation method thereof |
| CN113774220A (en) * | 2020-06-09 | 2021-12-10 | 杭州临安慧尔钼业科技有限公司 | Method for recovering molybdenum, bismuth and vanadium from waste catalysts of acrylic acid, methacrylic acid and esters thereof |
| CN115650293A (en) * | 2022-09-26 | 2023-01-31 | 西部鑫兴稀贵金属有限公司 | Ammonium molybdate production method |
| CN116443931A (en) * | 2023-04-24 | 2023-07-18 | 安庆市月铜钼业有限公司 | Sodium molybdate production process and sodium molybdate production system |
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| CN102557212A (en) * | 2011-12-30 | 2012-07-11 | 金堆城钼业股份有限公司 | Method for treating and recycling molybdenum calcine water-washing waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102557212A (en) * | 2011-12-30 | 2012-07-11 | 金堆城钼业股份有限公司 | Method for treating and recycling molybdenum calcine water-washing waste water |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109775760A (en) * | 2019-03-11 | 2019-05-21 | 中国有色金属工业西安勘察设计研究院有限公司 | Ultralow potassium ammonium molybdate solution, ammonium molybdate solution derived product and preparation method thereof |
| CN109775760B (en) * | 2019-03-11 | 2021-10-01 | 中国有色金属工业西安勘察设计研究院有限公司 | Ultra-low potassium ammonium molybdate solution, ammonium molybdate solution derivative product and preparation method thereof |
| CN113774220A (en) * | 2020-06-09 | 2021-12-10 | 杭州临安慧尔钼业科技有限公司 | Method for recovering molybdenum, bismuth and vanadium from waste catalysts of acrylic acid, methacrylic acid and esters thereof |
| CN115650293A (en) * | 2022-09-26 | 2023-01-31 | 西部鑫兴稀贵金属有限公司 | Ammonium molybdate production method |
| CN116443931A (en) * | 2023-04-24 | 2023-07-18 | 安庆市月铜钼业有限公司 | Sodium molybdate production process and sodium molybdate production system |
| CN116443931B (en) * | 2023-04-24 | 2023-09-22 | 安庆市月铜钼业有限公司 | Sodium molybdate production process and sodium molybdate production system |
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