CN103553132B - 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 Mo resource recovery and reuse technology field, be specifically related to a kind of method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate.
Background technology
Tradition prepare in production of molybdic ammonium adopt pickling molybdenum calcining, ammonia to soak, acid is heavy, ammonia is molten, evaporative crystallization is prepared into ammonium dimolybdate, in pickling with acid is heavy can produce a large amount of acid ammonia nitrogen waste water, serious environment pollution in this art production process.
Washing molybdenum calcining produces ammonium dimolybdate technique, produces the drawback of the contaminate environment of ammonia nitrogen waste water owing to effectively can evade traditional technology.Become the world and praise highly one of prevailing technology 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, and on average can reach about 10g/L ~ 30g/L, pH value is about 3 ~ 4.Add China's existing calcining molybdenum concentrate quality level general lower, the waste residue after ammonia leaching is containing molybdenum amount up to more than 20% ~ 30%, and it is very low that washing molybdenum calcining produces ammonium dimolybdate molybdenum turnover ratio, had a strong impact on this technique further genralrlization and application.
Because China adopts existing technique pickling molybdenum calcining to produce ammonium tetramolybdate technique except heteroacid is heavy mostly.Therefore it is imperative that the waste water that the waste water, waste residue and the pickling molybdenum calcining that produce washing molybdenum calcining produce, waste residue and the heavy crystalline mother solution of acid carry out comprehensive treating process.The problems such as current is ion-exchange and extraction process for the method that the recovery of molybdenum in waste liquid is traditional, but these two kinds of methods all exist environmental protection and long processing period, regeneration difficulty.A kind of method reclaiming molybdenum is described in CN102557212 patent, the method the acid in molybdenum calcining washing waste water, production of molybdic ammonium process is sunk after crystalline mother solution and calcining molybdenum concentrate mixing to stir and obtain slurry, the pH value regulating slurry is 0.5 ~ 2.5, is then, under the condition of 70 DEG C ~ 100 DEG C, slurry agitation 1h ~ 3h is carried out cleanup acid treatment in temperature; Carry out solid-liquid separation to the slurry after cleanup acid treatment, filter cake separation obtained is sent in the Ammonia leaching of production of molybdic ammonium technique and is carried out ammonia leaching process, processes rear discharge up to standard in filtrate feeding Waste Water Treatment separation obtained.Although the method also can reclaim molybdenum preferably from washing waste water, but this technique purification capacity is poor, process is only had to be greater than the calcining molybdenum concentrate of 61% or grade more Gao Gengchun containing molybdenum amount, the requirement of final ammonium molybdate quality product could be met, preferably in production of molybdic ammonium technique, its Technological adaptability is poor in a word.
Reclaim after traditional method is oxygen-enriched air roasting method or the process of high pressure base cooking method for ammonia leaching waste residue molybdenum, then do ammonium molybdate and Sodium orthomolybdate.As high pressure alkaline leaching, technical process is:
A ammonia is washed: washed by higher-grade ammonia leaching residue ammoniacal liquor, guarantees that the molybdenum content in ammonia washery slag is stabilized in about 18.5%;
B ammonia soaks: ammonia washery slag soaks slag molybdenum content and is reduced to about 10.85% from about 18.5% after an ammonia leaching, and the average leaching yield of molybdenum is 47.65%;
C alkali soaks: the alkali leaching slag molybdenum content of the leaching slag after an ammonia leaching by a certain percentage after high pressure base leaching is reduced to less than 2% by original 10.85%, the average leaching yield of molybdenum is 87.72%, and after ammonia leaching, alkali leaching, the average leaching yield of the total molybdenum of former higher-grade ammonia leaching residue is 94%;
D filtration, purification: the ammonia leaching solution after being soaked by ammonia purifies, and alkali immersion liquid carries out Recovery Purifying by ion-exchange;
E acid is heavy: by after purification to carry out acid containing molybdenum liquid heavy, prepare ammonium tetramolybdate;
F drying and packaging: the ammonium tetramolybdate of preparation is carried out drying and packaging and obtains ammonium tetramolybdate product.
As can be seen from above: this technique subject matter is that operation is long, cost is high, uneconomical.
In addition, disclose " leaching the method reclaiming molybdenum from ammonia leaching residue " the method in CN101660045 patent mainly to be sieved by ammonia leaching residue, sodium carbonate is added respectively and water carries out stirring pulp in its screen overflow, be heated to 90 ~ 100 DEG C and add clorox, constant temperature stirs, and filters to obtain an alkali immersion liquid of molybdenum; In its screen underflow, add sodium carbonate again and water carries out stirring pulp, dropping walks the molybdenum alkali immersion liquid obtained, constant temperature 90 ~ 100 DEG C, dropwises, and filters 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 medicament consumption large due to temperature height clorox, and the concentration of the alkali immersion liquid molybdenum simultaneously leached is little, and after removal of impurities, evaporation concentration energy consumption is very large, and application prospect is not had an optimistic view of.
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 method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate.The present invention adopts the molybdenum calcining ammonia leaching waste residue adding in waste water and acid sink mother liquor and be mixed with molybdenum calcining, by liquid phase magnetization treatment, makes waste water, the Mo resource of waste residue obtains efficiency utilization, makes filtrate return meet the requirement of environmental protection after the process of Conventional waste water treatment system simultaneously.Compare with washing waste water individual curing technique with ammonia leaching residue, ammonia leaching residue and the concentrated waste water of washing are directly used for production of molybdic ammonium by the present invention, significantly reduce molybdenum-containing waste slag, cost for wastewater treatment, not only energy-saving and environmental protection, and effectively improve the concentrated waste water of molybdenum calcining washing and ammonia leaching waste residue Mo resource utilization ratio, there is facility investment not high, process efficient, the features such as practicality.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate, and it is characterized in that, the method comprises the following steps:
Step one, 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 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, in washing molybdenum calcining ammonia leaching waste residue, add molybdenum calcining, then under agitation the washing molybdenum calcining ammonia leaching waste residue being added with molybdenum calcining is added in mixed solution described in step one, obtain solidliquid mixture, the pH value of described solidliquid mixture is regulated to be 0.5 ~ 1.5, again magnetization treatment is carried out to the solidliquid mixture after adjust ph, finally by the stirring reaction 30min ~ 90min at 50 DEG C ~ 70 DEG C of the solidliquid mixture after magnetization treatment, obtain solid-liquid mixed slurry; The addition of described molybdenum calcining is 60% ~ 80% of washing molybdenum calcining ammonia leaching waste residue and molybdenum calcining total mass; The liquid-solid ratio of described solidliquid mixture is (2 ~ 5): 1;
Step 3, solid-liquid separation is carried out to the mixed slurry of solid-liquid described in step 2, send in the Ammonia leaching of production of molybdic ammonium technique carry out ammonia leaching process by being separated the filter cake obtained;
Step 4, in step 3 ammonia leaching process after material 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 production of molybdic ammonium technique Ammonia leaching in carry out ammonia leaching process, then solid-liquid separation being carried out to the material after ammonia leaching process, returning in Ammonia leaching described in step 3 by being separated the filtrate obtained;
Step 6, employing ion-exchange carry out removal of impurities to ammonia leaching solution described in step 4, then adopt electric drive membrane separation apparatus to purify the ammonia leaching solution after removal of impurities, by heavy for the ammonia leaching solution acid after purification, obtain solid ammonium tetramolybdate after filtration.
A kind of above-mentioned method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate, the mass percentage adding molybdenum in the washing molybdenum calcining ammonia leaching waste residue before molybdenum calcining in step 2 is 15% ~ 30%.
A kind of above-mentioned method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate, the magneticstrength of magnetization treatment described in step 2 is not less than 25 kilogausss, and the magnetization treatment time is 10min ~ 30min.
A kind of above-mentioned method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate, the equipment that solid-liquid separation described in step 3 adopts is frame vacuum filtration machine.
A kind of above-mentioned method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate, the temperature of the leaching of ammonia described in step 3 process is 60 DEG C ~ 70 DEG C, and pH value is 8.5 ~ 9.5, and liquid-solid ratio is (2 ~ 5): 1, and the treatment time is 1h ~ 3h.
A kind of above-mentioned method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate, in filter cake described in step 3, the insoluble molybdenum mass percentage of ammonia is not more than 2.0%.
A kind of above-mentioned method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate, the equipment that solid-liquid separation described in step 4 adopts is wind pressure type paper blotter press.
A kind of above-mentioned method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate, the equipment that solid-liquid separation described in step 5 adopts is the diaphragm filter press of band washing.
A kind of above-mentioned method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate, 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 the molybdenum calcining ammonia leaching waste residue adding in waste water and acid sink mother liquor and be mixed with molybdenum calcining, by liquid phase magnetization treatment, make waste water, the Mo resource of waste residue obtains efficiency utilization, make filtrate return meet the requirement of environmental protection after the process of Conventional waste water treatment system simultaneously.
2, compare with washing waste water individual curing technique with ammonia leaching residue, ammonia leaching residue and the concentrated waste water of washing are directly used for production of molybdic ammonium by the present invention, significantly reduce molybdenum-containing waste slag, cost for wastewater treatment, not only energy-saving and environmental protection, and effectively improve the concentrated waste water of molybdenum calcining washing and ammonia leaching waste residue Mo resource utilization ratio, there is facility investment not high, process efficient, the features such as practicality.
3, the present invention prepares in ammonium molybdate process at waste water and dregs first and uses magnetization impurity elimination technology and electricity to tend to act membrane separation for removing impurities technology, potassium content in product is made to be less than 10ppm, quality reaches international most advanced level, domestic production of molybdic ammonium waste residue, waste water reclamation molybdenum technology and technique are promoted from extensive, scalar type to the transformation of meticulous type, mass type, improve China rich molybdenum waste water, waste residue Mo resource comprehensive reutilization level, indicate that rich molybdenum waste water, waste residue recycling has gone up a brand-new step.
4, energy system of the present invention solves the recovery and reuse problem of rich molybdenum washing waste water and the ammonia leaching residue molybdenum produced in molybdenum in China acid ammonium production process.The metal that minimizing pilot process produces because of waste water, waste residue occupies, and what produce in elimination production of molybdic ammonium line waste water treatment process contains molybdenum waste material and ammonia leaching residue warehousing pressure, significant to the turnover ratio and Mo resource utilization ratio improving molybdenum.
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment
Embodiment 1
Step one, concentrated by molybdenum calcining washing waste water, in the waste water after concentrated, primary metal ion concentration is: Mo93.54g/L, Cu0.12g/L, Fe3.29mg/L, K0.27g/L, Na0.18g/L, Ca0.91mg/L, Mg3.50mg/L; Then the molybdenum calcining washing waste water after concentrated and the acid in production of molybdic ammonium process are sunk crystalline mother solution by 1: 1 volume ratio mix, obtain mixed solution, in the heavy mother liquor of acid, primary metal ion concentration is: Mo6.06g/L, Cu0.006g/L, Fe1.09mg/L, K0.074g/L, Na0.17g/L, Ca0.021g/L, Mg0.04mg/L;
Step 2, to the mass percentage of Mo be 21.7% washing molybdenum calcining ammonia leaching waste residue in add molybdenum calcining, in molybdenum calcining, major metal mass content is: Mo63.38%, Cu0.09%, Fe1.18%, K0.07%, Na0.018%, Ca0.25%; Then under agitation the washing molybdenum calcining ammonia leaching waste residue being added with molybdenum calcining is added in mixed solution described in step one, obtain solidliquid mixture, the pH value of described solidliquid mixture is regulated to be 0.5, again magnetization treatment is carried out to the solidliquid mixture after adjust ph, finally by the stirring reaction 30min at 50 DEG C of the solidliquid mixture after magnetization treatment, obtain solid-liquid mixed slurry; The addition of described molybdenum calcining is 70% of washing molybdenum calcining ammonia leaching waste residue and molybdenum calcining total mass; The liquid-solid ratio (mass ratio) of described solidliquid mixture is 3: 1; The magneticstrength of described magnetization treatment 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 obtain separation 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 mass percentage of the insoluble molybdenum of ammonia is 1.7%; The pH value of filtrate is 0.5, and in filtrate, primary metal ion concentration is: Mo0.60g/L, Cu0.92g/L, Fe0.14mg/L, K0.30g/L, Na0.18g/L, Ca0.61g/L, Mg1.49mg/L; Filter cake separation obtained is sent in the Ammonia leaching of production of molybdic ammonium technique and is carried out ammonia leaching process, and the temperature that ammonia leaching processes is 65 DEG C, 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 process rear discharge up to standard, realize the recycling of the concentrated waste water of molybdenum calcining washing and ammonia leaching residue molybdenum;
Step 4, employing wind pressure type paper blotter press carry out solid-liquid separation to the material after ammonia leaching process in step 3, obtain ammonia leaching solution and ammonia leaching residue, after testing, in ammonia leaching solution, primary metal ion concentration 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 mass percentage of Mo is 19.10%, and the mass percentage of the insoluble molybdenum of ammonia is 1.60%;
Step 5, ammonia leaching residue described in step 4 is sent into production of molybdic ammonium technique Ammonia leaching in carry out ammonia leaching process, then the diaphragm filter press of band washing is adopted to carry out solid-liquid separation to the material after ammonia leaching process, return in Ammonia leaching described in step 3 by being separated the filtrate obtained, focus on being separated the filter residue feeding slag field obtained, after testing, in filter residue, the mass percentage of Mo is 6.2%, and the mass percentage of the insoluble molybdenum of ammonia is 1.5%;
Step 6, employing TP207 duplicate removal metal macropore chelating positive 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 primary metal ion concentration is: Mo150.07g/L, Cu0.003g/L, Fe5.0mg/L, K0.192g/L, Na0.092g/L, Ca3.01mg/L, Mg1.51mg/L; Then electric drive membrane separation apparatus is adopted, utilize electromotive force to order about alkali metal cation in ammonia leaching solution to cross diaphragm and purify the ammonia leaching solution after removal of impurities, ammonia leaching solution sampling after purification is detected, its primary metal ion concentration is Mo150.07g/L, Cu2.9mg/L, Fe4.50mg/L, K0.020g/L, Na0.012g/L, Ca3.0mg/L, Mg1.5mg/L; Filter after heavy for the ammonia leaching solution acid after purification, to filtering the filtrate that obtains and ammonium tetramolybdate filter cake samples detection respectively, 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, primary metal ion concentration is Mo7.12g/L, Cu0.5mg/L, Fe1.03mg/L, K0.024g/L, Na0.016g/L, Ca0.002g/L, Mg0.06mg/L.
The present embodiment adopts the molybdenum calcining ammonia leaching waste residue adding in waste water and acid sink mother liquor and be mixed with molybdenum calcining, by liquid phase magnetization treatment, make waste water, the Mo resource of waste residue obtains efficiency utilization, make filtrate return meet the requirement of environmental protection after the process of Conventional waste water treatment system simultaneously, compare with washing waste water individual curing technique with ammonia leaching residue, ammonia leaching residue and the concentrated waste water of washing are directly used for production of molybdic ammonium by the present embodiment, significantly reduce molybdenum-containing waste slag, cost for wastewater treatment, not only energy-conservation, environmental protection, and effectively improve the concentrated waste water of molybdenum calcining washing and ammonia leaching waste residue Mo resource utilization ratio, there is facility investment not high, process efficient, the features such as practicality.
Comparative example 1
Adopt ammonia leaching solution described in embodiment 1 step 4 directly to carry out acid to sink, sample detection respectively to filtrate and ammonium tetramolybdate filter cake after filtration, 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, primary metal ion concentration 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 one, concentrated by molybdenum calcining washing waste water, in the waste water after concentrated, primary metal ion concentration is: Mo90g/L, Cu0.13g/L, Fe3.28mg/L, K0.27g/L, Na0.15g/L, Ca0.90mg/L, Mg3.50mg/L; Then the molybdenum calcining washing waste water after concentrated and the acid in production of molybdic ammonium process are sunk crystalline mother solution by 1: 0.5 volume ratio mix, obtain mixed solution, in the heavy mother liquor of acid, primary metal ion concentration is: Mo6.06g/L, Cu0.006g/L, Fe1.09mg/L, K0.074g/L, Na0.17g/L, Ca0.021g/L, Mg0.04mg/L;
Step 2, to the mass percentage of Mo be 30% washing molybdenum calcining ammonia leaching waste residue in add molybdenum calcining, in molybdenum calcining, major metal mass content is: Mo63.35%, Cu0.088%, Fe1.15%, K0.08%, Na0.018%, Ca0.275%; Then under agitation the washing molybdenum calcining ammonia leaching waste residue being added with molybdenum calcining is added in mixed solution described in step one, obtain solidliquid mixture, the pH value of described solidliquid mixture is regulated to be 1.5, again magnetization treatment is carried out to the solidliquid mixture after adjust ph, finally by the stirring reaction 60min at 70 DEG C of the solidliquid mixture after magnetization treatment, obtain solid-liquid mixed slurry; The addition of described molybdenum calcining is 60% of washing molybdenum calcining ammonia leaching waste residue and molybdenum calcining total mass; The liquid-solid ratio (mass ratio) of described solidliquid mixture is 2: 1; The magneticstrength of described magnetization treatment 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 obtain separation 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 mass percentage of the insoluble molybdenum of ammonia is 2.0%; The pH value of filtrate is 0.5, and in filtrate, primary metal ion concentration is: Mo0.61g/L, Cu0.95g/L, Fe0.135mg/L, K0.31g/L, Na0.18g/L, Ca0.602g/L, Mg1.48mg/L; Filter cake separation obtained is sent in the Ammonia leaching of production of molybdic ammonium technique and is carried out ammonia leaching process, and the temperature that ammonia leaching processes is 60 DEG C, 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 process rear discharge up to standard, realize the recycling of the concentrated waste water of molybdenum calcining washing and ammonia leaching residue molybdenum;
Step 4, employing wind pressure type paper blotter press carry out solid-liquid separation to the material after ammonia leaching process in step 3, obtain ammonia leaching solution and ammonia leaching residue, after testing, in ammonia leaching solution, primary metal ion concentration 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 mass percentage of Mo is 18.1%, and the mass percentage of the insoluble molybdenum of ammonia is 1.90%;
Step 5, ammonia leaching residue described in step 4 is sent into production of molybdic ammonium technique Ammonia leaching in carry out ammonia leaching process, then the diaphragm filter press of band washing is adopted to carry out solid-liquid separation to the material after ammonia leaching process, return in Ammonia leaching described in step 3 by being separated the filtrate obtained, focus on being separated the filter residue feeding slag field obtained, after testing, in filter residue, the mass percentage of Mo is 4.1%, and the mass percentage of the insoluble molybdenum of ammonia is 2.3%;
Step 6, employing TP207 duplicate removal metal macropore chelating positive 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 primary metal ion concentration is: Mo152.28g/L, Cu2.8mg/L, Fe4.0mg/L, K0.19g/L, Na0.092g/L, Ca3.05mg/L, Mg1.45mg/L; Then electric drive membrane separation apparatus is adopted, utilize electromotive force to order about alkali metal cation in ammonia leaching solution to cross diaphragm and purify the ammonia leaching solution after removal of impurities, ammonia leaching solution sampling after purification is detected, its primary metal ion concentration is Mo152.28g/L, Cu2.6mg/L, Fe3.40mg/L, K0.018g/L, Na0.01g/L, Ca2.5mg/L, Mg1.42mg/L; Filter after heavy for the ammonia leaching solution acid after purification, to filtering the filtrate that obtains and ammonium tetramolybdate filter cake samples detection respectively, 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, primary metal ion concentration is Mo7.01g/L, Cu0.5mg/L, Fe1.12mg/L, K0.02g/L, Na0.016g/L, Ca0.0022g/L, Mg0.057mg/L.
The present embodiment adopts the molybdenum calcining ammonia leaching waste residue adding in waste water and acid sink mother liquor and be mixed with molybdenum calcining, by liquid phase magnetization treatment, make waste water, the Mo resource of waste residue obtains efficiency utilization, make filtrate return meet the requirement of environmental protection after the process of Conventional waste water treatment system simultaneously, compare with washing waste water individual curing technique with ammonia leaching residue, ammonia leaching residue and the concentrated waste water of washing are directly used for production of molybdic ammonium by the present embodiment, significantly reduce molybdenum-containing waste slag, cost for wastewater treatment, not only energy-conservation, environmental protection, and effectively improve the concentrated waste water of molybdenum calcining washing and ammonia leaching waste residue Mo resource utilization ratio, there is facility investment not high, process efficient, the features such as practicality.
Comparative example 2
Adopt ammonia leaching solution described in embodiment 2 step 4 directly to carry out acid to sink, sample detection respectively to filtrate and ammonium tetramolybdate filter cake after filtration, 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, primary metal ion concentration 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 one, concentrated by molybdenum calcining washing waste water, in the waste water after concentrated, primary metal ion concentration is: Mo95g/L, Cu0.15g/L, Fe3.32mg/L, K0.29g/L, Na0.15g/L, Ca0.88mg/L, Mg3.42mg/L; Then the molybdenum calcining washing waste water after concentrated and the acid in production of molybdic ammonium process are sunk crystalline mother solution by 1: 2 volume ratio mix, obtain mixed solution, in the heavy mother liquor of acid, primary metal ion concentration is: Mo6.06g/L, Cu0.006g/L, Fe1.09mg/L, K0.074g/L, Na0.17g/L, Ca0.021g/L, Mg0.04mg/L;
Step 2, to the mass percentage of Mo be 15% washing molybdenum calcining ammonia leaching waste residue in add molybdenum calcining, in molybdenum calcining, major metal mass content is: Mo63.38%, Cu0.09%, Fe1.18%, K0.07%, Na0.018%, Ca0.25%; Then under agitation the washing molybdenum calcining ammonia leaching waste residue being added with molybdenum calcining is added in mixed solution described in step one, obtain solidliquid mixture, the pH value of described solidliquid mixture is regulated to be 1.0, again magnetization treatment is carried out to the solidliquid mixture after adjust ph, finally by the stirring reaction 90min at 60 DEG C of the solidliquid mixture after magnetization treatment, obtain solid-liquid mixed slurry; The addition of described molybdenum calcining is 80% of washing molybdenum calcining ammonia leaching waste residue and molybdenum calcining total mass; The liquid-solid ratio (mass ratio) of described solidliquid mixture is 5: 1; The magneticstrength of described magnetization treatment 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 obtain separation 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 mass percentage of the insoluble molybdenum of ammonia is 1.9%; The pH value of filtrate is 0.5, and in filtrate, primary metal ion concentration is: Mo0.61g/L, Cu0.92g/L, Fe0.15mg/L, K0.32g/L, Na0.16g/L, Ca0.60g/L, Mg1.45mg/L; Filter cake separation obtained is sent in the Ammonia leaching of production of molybdic ammonium technique and is carried out ammonia leaching process, and the temperature that ammonia leaching processes is 70 DEG C, 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 process rear discharge up to standard, realize the recycling of the concentrated waste water of molybdenum calcining washing and ammonia leaching residue molybdenum;
Step 4, employing wind pressure type paper blotter press carry out solid-liquid separation to the material after ammonia leaching process in step 3, obtain ammonia leaching solution and ammonia leaching residue, after testing, in ammonia leaching solution, primary metal ion concentration 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 mass percentage of Mo is 21.1%, and the mass percentage of the insoluble molybdenum of ammonia is 1.70%;
Step 5, ammonia leaching residue described in step 4 is sent into production of molybdic ammonium technique Ammonia leaching in carry out ammonia leaching process, then the diaphragm filter press of band washing is adopted to carry out solid-liquid separation to the material after ammonia leaching process, return in Ammonia leaching described in step 3 by being separated the filtrate obtained, focus on being separated the filter residue feeding slag field obtained, after testing, in filter residue, the mass percentage of Mo is 5.5%, and the mass percentage of the insoluble molybdenum of ammonia is 2.2%;
Step 6, employing TP207 duplicate removal metal macropore chelating positive 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 primary metal ion concentration is: Mo150.75g/L, Cu3.2mg/L, Fe5.1mg/L, K0.190g/L, Na0.092g/L, Ca3.03mg/L, Mg1.45mg/L; Then electric drive membrane separation apparatus is adopted, utilize electromotive force to order about alkali metal cation in ammonia leaching solution to cross diaphragm and purify the ammonia leaching solution after removal of impurities, ammonia leaching solution sampling after purification is detected, its primary metal ion concentration is Mo150.75g/L, Cu3.0mg/L, Fe4.64mg/L, K0.018g/L, Na0.012g/L, Ca2.9mg/L, Mg1.41mg/L; Filter after heavy for the ammonia leaching solution acid after purification, to filtering the filtrate that obtains and ammonium tetramolybdate filter cake samples detection respectively, 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, primary metal ion concentration is Mo7.35g/L, Cu0.7mg/L, Fe1.05mg/L, K0.02g/L, Na0.018g/L, Ca0.002g/L, Mg0.057mg/L.
The present embodiment adopts the molybdenum calcining ammonia leaching waste residue adding in waste water and acid sink mother liquor and be mixed with molybdenum calcining, by liquid phase magnetization treatment, make waste water, the Mo resource of waste residue obtains efficiency utilization, make filtrate return meet the requirement of environmental protection after the process of Conventional waste water treatment system simultaneously, compare with washing waste water individual curing technique with ammonia leaching residue, ammonia leaching residue and the concentrated waste water of washing are directly used for production of molybdic ammonium by the present embodiment, significantly reduce molybdenum-containing waste slag, cost for wastewater treatment, not only energy-conservation, environmental protection, and effectively improve the concentrated waste water of molybdenum calcining washing and ammonia leaching waste residue Mo resource utilization ratio, there is facility investment not high, process efficient, the features such as practicality.
Comparative example 3
Adopt ammonia leaching solution described in embodiment 3 step 4 directly to carry out acid to sink, sample detection respectively to filtrate and ammonium tetramolybdate filter cake after filtration, 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, primary metal ion concentration 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 can be found out with the data of comparative example 3 with comparative example 2 and embodiment 3, the present invention adopts ion-exchange removal of impurities to tend to act membrane sepn purification techniques in conjunction with electricity, effectively can remove the impurity metal content in product, potassium content in product is made to be less than 10ppm, quality reaches international most advanced level, promote 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, improve the rich molybdenum waste water of China, waste residue Mo resource comprehensive reutilization 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 any restriction is done to the present invention, every above embodiment is done according to invention technical spirit any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (8)
1. process the method that ammonium tetramolybdate prepared by rich molybdenum waste water waste residue, it is characterized in that, the method comprises the following steps:
Step one, 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 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, in washing molybdenum calcining ammonia leaching waste residue, add molybdenum calcining, then under agitation the washing molybdenum calcining ammonia leaching waste residue being added with molybdenum calcining is added in mixed solution described in step one, obtain solidliquid mixture, the pH value of described solidliquid mixture is regulated to be 0.5 ~ 1.5, again magnetization treatment is carried out to the solidliquid mixture after adjust ph, finally by the stirring reaction 30min ~ 90min at 50 DEG C ~ 70 DEG C of the solidliquid mixture after magnetization treatment, obtain solid-liquid mixed slurry; The addition of described molybdenum calcining is 60% ~ 80% of washing molybdenum calcining ammonia leaching waste residue and molybdenum calcining total mass; The liquid-solid ratio of described solidliquid mixture is counted (2 ~ 5) in mass ratio: 1; The magneticstrength of described magnetization treatment is not less than 25 kilogausss, and the magnetization treatment time is 10min ~ 30min;
Step 3, solid-liquid separation is carried out to the mixed slurry of solid-liquid described in step 2, send in the Ammonia leaching of production of molybdic ammonium technique carry out ammonia leaching process by being separated the filter cake obtained;
Step 4, in step 3 ammonia leaching process after material 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 production of molybdic ammonium technique Ammonia leaching in carry out ammonia leaching process, then solid-liquid separation being carried out to the material after ammonia leaching process, returning in Ammonia leaching described in step 3 by being separated the filtrate obtained;
Step 6, employing ion-exchange carry out removal of impurities to ammonia leaching solution described in step 4, then adopt electric drive membrane separation apparatus to purify the ammonia leaching solution after removal of impurities, by heavy for the ammonia leaching solution acid after purification, obtain solid ammonium tetramolybdate after filtration.
2. a kind of method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate according to claim 1, is characterized in that, the mass percentage adding molybdenum in the washing molybdenum calcining ammonia leaching waste residue before molybdenum calcining in step 2 is 15% ~ 30%.
3. a kind of method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate according to claim 1, is characterized in that, the equipment that solid-liquid separation described in step 3 adopts is frame vacuum filtration machine.
4. a kind of method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate according to claim 1, it is characterized in that, the temperature of the leaching of ammonia described in step 3 process is 60 DEG C ~ 70 DEG C, and pH value is 8.5 ~ 9.5, liquid-solid ratio is counted in mass ratio (2 ~ 5): 1, and the treatment time is 1h ~ 3h.
5. a kind of method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate according to claim 1, it is characterized in that, in filter cake described in step 3, the insoluble molybdenum mass percentage of ammonia is not more than 2.0%.
6. a kind of method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate 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.
7. a kind of method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate 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.
8. a kind of method processing rich molybdenum waste water waste residue and prepare ammonium tetramolybdate 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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