CN108706634B - Apparatus and method for purifying ammonium tungstate solution - Google Patents
Apparatus and method for purifying ammonium tungstate solution Download PDFInfo
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- CN108706634B CN108706634B CN201810598563.3A CN201810598563A CN108706634B CN 108706634 B CN108706634 B CN 108706634B CN 201810598563 A CN201810598563 A CN 201810598563A CN 108706634 B CN108706634 B CN 108706634B
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Abstract
The invention discloses a device and a method for purifying ammonium tungstate solution, wherein the device comprises: the equipment comprises an equipment body, wherein a feeding area, an adsorption area, an exchange area and a discharging area are defined in the equipment body from top to bottom, the adsorption area is filled with activated carbon, and the exchange area is filled with resin; a first distribution plate disposed between the feed zone and the activated carbon adsorption zone; the second distribution plate is arranged between the activated carbon adsorption area and the resin exchange area; the third distribution plate is arranged between the resin exchange area and the discharging area; an ammonium tungstate solution inlet, which is arranged in the feeding area; an exhaust port disposed in the feed zone; the export of ammonium tungstate solution after purifying, it establishes to purify the export of ammonium tungstate solution after the purification ejection of compact district. By adopting the equipment, the ultra-high purity ammonium tungstate solution with the tungsten-molybdenum ratio of more than 50000 can be obtained, and the economic benefit of enterprises is obviously improved.
Description
Technical Field
The invention belongs to the field of tungsten smelting, and particularly relates to equipment and a method for purifying an ammonium tungstate solution.
Background
Tungsten and molybdenum are important strategic rare metals in China and have wide application in industry. Tungsten and molybdenum belong to VIB group in the periodic table of elements, and are influenced by lanthanide contraction, and the atomic radii, atomic structures and chemical properties of the tungsten and the molybdenum are extremely similar, so that the separation process is difficult. Tungsten and molybdenum in a plurality of associated tungsten and molybdenum element resources exist in the same phase in terms of quality, and currently, the tungsten and molybdenum elements cannot be effectively separated by adopting a common beneficiation method, and only the tungsten and molybdenum elements can be treated by adopting a metallurgical process. The current tungsten-molybdenum separation patent technology mainly adopts a precipitation separation method, an ion exchange separation method and a solvent extraction separation method, and in the actual production process of tungsten metallurgy at the present stage, the actual tungsten-molybdenum separation effect of various tungsten-molybdenum separation technologies is different from the application range thereof, and the corresponding separation effects are also different. Generally, the molar concentration ratio of tungsten and molybdenum in the solution after molybdenum removal can be within the range of 2500-12500 due to different molar concentration ratios of tungsten and molybdenum in the initial tungsten molybdate mixed solution, and at the moment, the molybdenum content in the solution cannot be further reduced by means of the tungsten and molybdenum separation technology, so that the impurity purity of the subsequent APT product is restricted; secondly, tiny particle impurities in the solution enter the solution after molybdenum removal with a certain probability in the tungsten-molybdenum separation process, and the phenomena of co-crystallization, agglomeration and the like occur in the crystallization process, so that the impurities of the APT product exceed the standard or carry impurity particles such as black spots and the like, and the bottleneck of improving the product quality of production enterprises is formed.
Thus, the existing techniques for processing tungsten molybdates are in need of further improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose an apparatus and a method for purifying an ammonium tungstate solution. By adopting the equipment, the ultra-high purity ammonium tungstate solution with the tungsten-molybdenum ratio of more than 50000 can be obtained, and the economic benefit of enterprises is obviously improved.
In one aspect of the present invention, there is provided an apparatus for purifying an ammonium tungstate solution, the apparatus including, according to an embodiment of the present invention:
the equipment comprises an equipment body, wherein a feeding area, an adsorption area, an exchange area and a discharging area are defined in the equipment body from top to bottom, the adsorption area is filled with activated carbon, and the exchange area is filled with resin;
a first distribution plate disposed between the feed zone and the activated carbon adsorption zone;
the second distribution plate is arranged between the activated carbon adsorption area and the resin exchange area;
the third distribution plate is arranged between the resin exchange area and the discharging area;
an ammonium tungstate solution inlet, which is arranged in the feeding area;
an exhaust port disposed in the feed zone;
the export of ammonium tungstate solution after purifying, it establishes to purify the export of ammonium tungstate solution after the purification ejection of compact district.
According to the equipment for purifying the ammonium tungstate solution, the ammonium tungstate solution enters the equipment body through an ammonium tungstate solution inlet located in a feeding area of the equipment body, and sequentially passes through an adsorption area filled with activated carbon and an exchange area filled with resin under the action of gravity and a first distribution plate, a second distribution plate and a third distribution plate, the ammonium tungstate solution can fully soak the activated carbon in the adsorption area under the action of the first distribution plate and the second distribution plate, the activated carbon adsorbs impurities in the ammonium tungstate solution, then the ammonium tungstate solution subjected to impurity adsorption by the activated carbon enters the exchange area under the action of gravity and the second distribution plate and the third distribution plate, the resin in the exchange area is fully soaked, and the resin achieves the purpose of purifying the ammonium tungstate solution by adsorbing the impurities in the ammonium tungstate solution. After activated carbon adsorption and resin exchange impurity removal, the purified ammonium tungstate solution with the tungsten-molybdenum ratio of more than 50000 can be obtained, high-purity APT products with the purity of more than 99.999 percent can be produced and far exceed APT international zero-order product standards, and because the ammonium tungstate solution is in a closed environment in the whole process and does not contact external pollution, the phenomena that impurities of subsequent APT products exceed standards or black spots occur can be effectively avoided, the loss of production enterprises caused by the fact that the impurities of APT exceed standards is avoided, meanwhile, the whole equipment is simple and convenient to operate, low in investment cost and remarkable in economic benefit.
In addition, the apparatus for purifying an ammonium tungstate solution according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, a flow meter is arranged at the outlet of the purified ammonium tungstate solution. Therefore, the adsorption flow of the ammonium tungstate solution in the equipment for purifying the ammonium tungstate solution can be adjusted in real time.
In some embodiments of the invention, the activated carbon loading of the adsorption zone is 80% to 85% of the volume of the adsorption zone. Therefore, the damage to equipment caused by volume expansion after the ammonium tungstate solution is soaked by the activated carbon can be avoided.
In some embodiments of the invention, the resin fill of the exchange zone is 80% to 85% of the exchange zone volume. Therefore, damage to equipment caused by swelling after the resin is soaked in the ammonium tungstate solution can be avoided.
In some embodiments of the invention, the height ratio of the adsorption zone to the exchange zone is from 1:1 to 1: 2. Therefore, the purification effect of the ammonium tungstate solution is improved.
In some embodiments of the invention, the first distribution plate, the second distribution plate, and the third distribution plate are each independently a water cap distribution plate. From this, be favorable to realizing the nimble regulation to equipment body internal adsorption zone and exchange area ammonium tungstate solution flow to further improve ammonium tungstate solution's purifying effect.
In some embodiments of the invention, the water cap distribution plate comprises: the water cap distribution plate is provided with a plurality of water cap mounting holes; the water cap comprises a cap body and a screw rod, one end of the screw rod is connected with the bottom of the cap body, a slit is formed in the cap body, and the other end of the screw rod is matched with the water cap mounting hole through a nut. Thereby, the purification effect of the ammonium tungstate solution can be further improved.
In some embodiments of the invention, the resin is a 001 x 7(Na form) strongly acidic cation exchange resin. Thereby, the purification effect of the ammonium tungstate solution can be further improved.
In still another aspect of the present invention, the present invention provides a method for purifying an ammonium tungstate solution using the above apparatus, the method including:
and feeding ammonium tungstate solution to the feeding area from an ammonium tungstate solution inlet, so that the ammonium tungstate solution sequentially passes through the activated carbon in the adsorption area and the resin in the exchange area to be soaked and adsorbed, so that purified ammonium tungstate solution is obtained, and the purified ammonium tungstate solution is discharged through a purified ammonium tungstate solution outlet.
According to the method for purifying the ammonium tungstate solution, the ammonium tungstate solution enters the equipment body through an ammonium tungstate solution inlet located in a feeding area of the equipment body, and sequentially passes through an adsorption area filled with activated carbon and an exchange area filled with resin under the action of gravity and a first distribution plate, a second distribution plate and a third distribution plate, the ammonium tungstate solution can fully soak the activated carbon in the adsorption area under the action of the first distribution plate and the second distribution plate, the activated carbon adsorbs impurities in the ammonium tungstate solution, then the ammonium tungstate solution subjected to impurity adsorption by the activated carbon enters the exchange area under the action of gravity and the second distribution plate and the third distribution plate, the resin in the exchange area is fully soaked, and the resin achieves the purpose of purifying the ammonium tungstate solution by adsorbing the impurities in the ammonium tungstate solution. After activated carbon adsorption and resin exchange impurity removal, the purified ammonium tungstate solution with the tungsten-molybdenum ratio of more than 50000 can be obtained, high-purity APT products with the purity of more than 99.999 percent can be produced and far exceed APT international zero-order product standards, and because the ammonium tungstate solution is in a closed environment in the whole process and does not contact external pollution, the phenomena that impurities of subsequent APT products exceed standards or black spots occur can be effectively avoided, the loss of production enterprises caused by the fact that the impurities of APT exceed standards is avoided, meanwhile, the whole equipment is simple and convenient to operate, low in investment cost and remarkable in economic benefit.
In addition, the method for purifying the ammonium tungstate solution according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, after the activated carbon and the resin are saturated by adsorption, the method further comprises: and supplying pure water through the ammonium tungstate solution inlet to carry out desorption treatment on the activated carbon and the resin so as to obtain desorption liquid, and discharging the desorption liquid through the purified ammonium tungstate solution outlet. Therefore, the regeneration and cyclic utilization of the activated carbon and the resin can be realized, and the energy consumption of the process is further reduced.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic diagram of an apparatus for purifying an ammonium tungstate solution according to an embodiment of the present invention;
fig. 2 is a schematic structural view of a water cap mounting plate on a water cap distribution plate in an apparatus for purifying an ammonium tungstate solution according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a water cap structure on a water cap distribution plate in an apparatus for purifying an ammonium tungstate solution according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of an apparatus for purifying an ammonium tungstate solution according to still another embodiment of the present invention;
FIG. 5 is a schematic flow diagram of a method for purifying an ammonium tungstate solution, according to one embodiment of the invention;
fig. 6 is a schematic flow diagram of a method for purifying an ammonium tungstate solution according to still another embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the present invention, the present invention provides an apparatus for purifying an ammonium tungstate solution, which includes, according to an embodiment of the present invention, referring to fig. 1: the equipment comprises an equipment body 100, a first distribution plate 11, a second distribution plate 12, a third distribution plate 13, an ammonium tungstate solution inlet 101, an exhaust port 102 and a purified ammonium tungstate solution outlet 103.
According to the embodiment of the invention, a feeding zone 110, an adsorption zone 120, an exchange zone 130 and a discharging zone 140 are defined in the device body 100 from top to bottom, wherein the adsorption zone 120 is filled with activated carbon, and the exchange zone 130 is filled with resin. From this, from the top down has the feeding district in proper order in the equipment body, the active carbon adsorption district, resin exchange district and ejection of compact district, wherein the impurity in the ammonium tungstate solution can be adsorbed through the adsorption of active carbon in the active carbon adsorption district, for example the fine solid particle impurity in the ammonium tungstate solution and the part ion state impurity that exists with molybdenum's polymerization anion form, and can exchange out positive ion impurity in the ammonium tungstate solution such As lead (Pb), tin (Sn), antimony (Sb), arsenic (As) etc. under the exchange of resin in the resin exchange district, thereby reach the purpose of edulcoration, its principle is the functional sulfonic group (-SO) of resin3H) By substitution of cations such As lead (Pb), tin (Sn), antimony (Sb) and arsenic (As)And adsorbing to realize the effect of deep purification of the solution. The positions of the adsorption area and the exchange area can not be interchanged, and the adsorption area is positioned at the upper part of the purification column and can preferentially adsorb fine solid particles in the ammonium tungstate solution to prevent the fine solid particles from entering the exchange area filled with resin and covering the surface of the resin to block pores in the resin so as to influence the adsorption exchange effect of the resin; secondly, as the activated carbon is inevitably broken to different degrees along with the prolonging of the time in the using process to form activated carbon fragment particles, the resin filled in the exchange area positioned below can filter the fine-grained activated carbon fragment particles in time, and the pollution caused by the fact that the resin enters the subsequent flow along with the solution is prevented.
According to one embodiment of the present invention, an ammonium tungstate solution inlet 101 and a gas vent 102 are provided in the feed zone 110. From this, can conveniently add this clarification plant with ammonium tungstate solution, and can let ammonium tungstate solution pass through activated carbon adsorption district and resin exchange district in proper order under the effect of gravity to from ejection of compact district discharge apparatus, and need not external force, be favorable to reducing the energy consumption of equipment. And along with the in-process that ammonium tungstate solution descends, the gas that produces in the equipment body is from lower to upper, and the gas vent through the feeding district is in the same direction as the line and is discharged. It should be noted that, the ammonium tungstate solution may be subjected to a molybdenum removal process in advance before being introduced into the feeding area in the apparatus body from the ammonium tungstate solution inlet, for example, the ammonium tungstate solution may be subjected to ion exchange, separation, adsorption and impurity removal by using 201 × 7(Cl type) strongly basic anion exchange resin, so as to obtain an ammonium tungstate solution with a tungsten-molybdenum ratio of about 12500, thereby being beneficial to reducing the energy consumption of the apparatus for purifying the ammonium tungstate solution, improving the processing efficiency of the apparatus, simultaneously obtaining an ammonium tungstate solution with a higher tungsten-molybdenum ratio, and further being beneficial to obtaining an APT product with a higher purity. It should be noted that the specific positions of the ammonium tungstate solution inlet and the exhaust port in the feeding zone are not particularly limited, and those skilled in the art can select the ammonium tungstate solution inlet and the exhaust port according to actual needs.
According to yet another embodiment of the present invention, the activated carbon filling amount of the adsorption region 120 may be 80% to 85% of the volume of the adsorption region 120. The inventor finds that the volume of the activated carbon in the adsorption zone expands when the activated carbon is soaked by the ammonium tungstate solution, and if the filling amount of the activated carbon in the adsorption zone is too high, the volume of the expanded activated carbon is larger than that of the adsorption zone, so that excessive pressure is applied to the first distribution plate, the second distribution plate and the inner wall of the equipment body, and the service lives of the first distribution plate, the second distribution plate and the equipment body are shortened.
According to yet another embodiment of the present invention, the resin fill of the exchange region 130 is 80% to 85% of the volume of the exchange region 130. The inventors have found that the resin in the exchange zone is found to swell when soaked with ammonium tungstate solution, and if the resin filling amount in the exchange zone is too high, the volume of the resin after swelling will be greater than the volume of the exchange zone, thereby giving too much pressure to the second distribution plate, the third distribution plate and the inner wall of the apparatus body, and reducing the service life of the second distribution plate, the third distribution plate and the apparatus body.
According to yet another embodiment of the present invention, the height ratio of the adsorption zone 120 and the exchange zone 130 may be 1:1 to 1: 2. The inventor finds that the specific value of the height ratio of the adsorption area to the exchange area is determined by two factors of the amount of fine solid particle impurities in the ammonium tungstate solution and the composition and content of impurity ions, and a preferable height ratio range of the adsorption area to the exchange area is 1: 1-1: 2 according to earlier theoretical experiments and pilot plant test data of production.
According to yet another embodiment of the invention, the exchange zone packing resin is a 001 × 7(Na type) strongly acidic cation exchange resin. The inventors found that the adsorption order of a part of cations by a 001X 7(Na type) strongly acidic cation exchange resin is Fe3+>Al3+>Ra2+>Pb2+>Sr2+>Ca2+>Ni2+>Cd2+>Cu2+>Co2+>Zn2+>Mg2+>Ba2+>K+>NH4+>Na+>Li+The ammonium tungstate solution in the production process is sampled to find that the main cationic impurity is Fe3+、Sb2+、Pb2+Etc. and the 001X 7 resin has a strong adsorption capacity for the above cationic impurities, combined with the durability and current market price of the resin of this type, and in addition, its use conditions are low, the pretreatment operation is carried outThe method is simple and easy, so that 001X 7(Na type) strong-acid cation exchange resin is preferably used as the resin in the exchange area.
According to yet another embodiment of the present invention, a first distribution plate 11 is provided between the feed zone 110 and the activated carbon adsorption zone 120; the second distribution plate 12 is arranged between the activated carbon adsorption zone 120 and the resin exchange zone 130; a third distribution plate 13 is provided between the resin exchange zone 130 and the discharge zone 140. The first distribution plate and the second distribution plate are used for fixing activated carbon filled in the adsorption area, the second distribution plate and the third distribution plate are used for fixing resin filled in the exchange area, feed liquid is kept to flow from top to bottom through the purification column, and solution is adsorbed in the adsorption area in sequence and then is subjected to ion exchange in the exchange area to complete secondary purification.
According to another embodiment of the present invention, the first distribution plate 11, the second distribution plate 12 and the third distribution plate 13 may be water cap distribution plates, respectively. According to an embodiment of the present invention, referring to fig. 2 and 3, the water cap distribution plate includes a water cap mounting plate 21 and a water cap 22, the water cap mounting plate 21 is provided with a plurality of water cap mounting holes 211, the water cap 22 includes a cap body 221 and a screw 222, wherein one end of the screw 222 is connected to the bottom of the cap body 221, the cap body 221 is provided with a slit 223, and the other end of the screw 222 is matched with the water cap mounting holes 211 through a nut (not shown). According to a specific example of the present invention, the water cap 22 is an ABS water cap, the water cap mounting plate 21 is a carbon steel plastic lined water cap mounting plate, and the slits 223 on the water cap 22 are screw-shaped slits distributed along the outer circumferential surface of the water cap, and the slits 223 are also provided on the bottom of the water cap 22; the screw 222 is a hollow screw, and is communicated with the inside of the cap body 221. Specifically, use first distribution plate as the water cap distribution plate as the example, the slit that the ammonium tungstate solution that supplies to the feed area through ammonium tungstate solution entry gets into the internal portion of cap through the water cap on the water cap distribution plate, then supplies to the adsorption zone through the screw rod, through the dispersion of a plurality of water caps for ammonium tungstate solution disperses, thereby improves the effect at adsorption zone and active carbon.
According to yet another embodiment of the present invention, purified ammonium tungstate solution outlet 103 is disposed in discharge section 140. Therefore, the purified ammonium tungstate solution can be discharged from equipment in time, and the reaction is promoted. It should be noted that the specific position of the outlet of the purified ammonium tungstate solution in the discharge area is not particularly limited, and those skilled in the art can select the outlet according to actual needs.
According to another embodiment of the present invention, referring to fig. 4, a flow meter 14 may be provided at the outlet 103 of the purified ammonium tungstate solution. From this, can be according to the adsorption flow of the numerical value adjustment equipment body of flowmeter, with the single volume maximize that adsorbs the ammonium tungstate solution of handling when guaranteeing ammonium tungstate solution's purifying effect, and then reach the purpose that improve equipment purifies the efficiency that ammonium tungstate solution handled.
Specifically, before the ammonium tungstate solution is sent to the ammonium tungstate solution purification equipment, ion exchange separation, adsorption and impurity removal are carried out on the ammonium tungstate solution by using 201 × 7 (Cl-type) strongly basic anion exchange resin in advance to obtain a primary molybdenum-ammonium tungstate removal solution with a tungsten-molybdenum ratio of about 12500; and then the primary molybdenum-removing ammonium tungstate solution is sent to a feeding area from an ammonium tungstate solution inlet of the feeding area of the equipment body, the primary molybdenum-removing ammonium tungstate solution is distributed to an active carbon adsorption area through a first distribution plate, fine solid particle impurities and part of ionic impurities existing in a molybdenum polymerization anion state are adsorbed and removed by active carbon, then the primary molybdenum-removing ammonium tungstate solution is distributed to a resin exchange area through a second distribution plate, cationic impurities are exchanged and adsorbed and removed by 001 x 7 resin, the primary molybdenum-removing ammonium tungstate solution enters a discharging area after passing through a third distribution plate, and the purified ammonium tungstate solution is discharged from a purified ammonium tungstate solution outlet of the discharging area, so that a purified ammonium tungstate solution with a tungsten-molybdenum ratio of more than 50000 is obtained, the purified ammonium tungstate solution is used for producing an APT product through subsequent evaporative crystallization, and a high-purity APT product with a purity of more. The gas produced during the purification is discharged from the gas outlet of the feed zone. Along with the quantity increase of equipment processing ammonium tungstate solution, the active carbon in adsorption zone and the resin in exchange area are because of the constantly increase of impurity adsorption's volume, when being close to saturation, active carbon and resin deactivation, accessible ammonium tungstate solution entry is injected high pure water desorption active carbon and resin into the equipment body this moment, and the desorption liquid that obtains is retrieved, reciprocates many times until active carbon and resin regeneration, from this, realizes the cyclic utilization of active carbon and resin, and the input cost of showing reduction equipment.
According to the equipment for purifying the ammonium tungstate solution, the ammonium tungstate solution enters the equipment body through an ammonium tungstate solution inlet located in a feeding area of the equipment body, and sequentially passes through an adsorption area filled with activated carbon and an exchange area filled with resin under the action of gravity and a first distribution plate, a second distribution plate and a third distribution plate, the ammonium tungstate solution can fully soak the activated carbon in the adsorption area under the action of the first distribution plate and the second distribution plate, the activated carbon adsorbs impurities in the ammonium tungstate solution, then the ammonium tungstate solution subjected to impurity adsorption by the activated carbon enters the exchange area under the action of gravity and the second distribution plate and the third distribution plate, the resin in the exchange area is fully soaked, and the resin achieves the purpose of purifying the ammonium tungstate solution by adsorbing the impurities in the ammonium tungstate solution. After activated carbon adsorption and resin exchange impurity removal, the purified ammonium tungstate solution with the tungsten-molybdenum ratio of more than 50000 can be obtained, high-purity APT products with the purity of more than 99.999 percent can be produced and far exceed APT international zero-order product standards, and because the ammonium tungstate solution is in a closed environment in the whole process and does not contact external pollution, the phenomena that impurities of subsequent APT products exceed standards or black spots occur can be effectively avoided, the loss of production enterprises caused by the fact that the impurities of APT exceed standards is avoided, meanwhile, the whole equipment is simple and convenient to operate, low in investment cost and remarkable in economic benefit.
In a further aspect of the present invention, the present invention provides a method for purifying an ammonium tungstate solution using the above apparatus, and referring to fig. 5, the method includes:
s100: supply ammonium tungstate solution to the feeding area from ammonium tungstate solution entry, make ammonium tungstate solution soak, adsorb through the active carbon of adsorption zone and the resin in exchange area in proper order to obtain ammonium tungstate solution after purifying, and the ammonium tungstate solution after purifying that will obtain exports the discharge through ammonium tungstate solution after purifying
In this step, supply ammonium tungstate solution to the feeding area from ammonium tungstate solution entry, make ammonium tungstate solution soak, adsorb through the active carbon of adsorption zone and the resin in exchange area in proper order to obtain the ammonium tungstate solution after purifying, and will obtain the ammonium tungstate solution after purifying export discharge of ammonium tungstate solution after purifying. Specifically, is provided withThe device body is internally provided with a feeding area, an active carbon adsorption area, a resin exchange area and a discharging area from top to bottom in sequence, wherein impurities in the ammonium tungstate solution, such as fine solid particle impurities in the ammonium tungstate solution and ionic impurities partially existing in a molybdenum polymeric anion form, can be adsorbed in the active carbon adsorption area through the adsorption effect of active carbon; the inventor finds that the cation impurities in the ammonium tungstate solution, such As lead (Pb), tin (Sn), antimony (Sb), arsenic (As) and the like, can be exchanged under the exchange action of the resin in the resin exchange zone SO As to achieve the purpose of impurity removal, and the principle of the method is that the functional group sulfonic acid group (-SO) of the resin is used As the principle of exchanging the cation impurities in the ammonium tungstate solution, such As lead (Pb), tin (Sn), antimony (Sb), arsenic (As) and the like, under the exchange action of the resin in the resin exchange zone SO As to achieve the purpose of impurity removal3H) The method has the function of realizing the deep purification of the solution by replacing and adsorbing cations such As lead (Pb), tin (Sn), antimony (Sb), arsenic (As) and the like. The positions of the adsorption area and the exchange area can not be interchanged, and the adsorption area is positioned at the upper part of the purification column and can preferentially adsorb fine solid particles in the ammonium tungstate solution to prevent the fine solid particles from entering the exchange area filled with resin and covering the surface of the resin to block pores in the resin so as to influence the adsorption exchange effect of the resin; secondly, as the activated carbon is inevitably broken to different degrees along with the prolonging of the time in the using process to form activated carbon fragment particles, the resin filled in the exchange area positioned below can filter the fine-grained activated carbon fragment particles in time, and the pollution caused by the fact that the resin enters the subsequent flow along with the solution is prevented. It should be noted that, the ammonium tungstate solution may be subjected to a molybdenum removal process in advance before being introduced into the feeding area in the apparatus body from the ammonium tungstate solution inlet, for example, the ammonium tungstate solution may be subjected to ion exchange, separation, adsorption and impurity removal by using 201 × 7(Cl type) strongly basic anion exchange resin, so as to obtain an ammonium tungstate solution with a tungsten-molybdenum ratio of about 12500, thereby being beneficial to reducing the energy consumption of the apparatus for purifying the ammonium tungstate solution, improving the processing efficiency of the apparatus, simultaneously obtaining an ammonium tungstate solution with a higher tungsten-molybdenum ratio, and further being beneficial to obtaining an APT product with a higher purity.
According to one embodiment of the invention, the exchange zone packing resin is 001X 7(Na type) strong acidAn anionic cation exchange resin. The inventors found that the adsorption order of a part of cations by a 001X 7(Na type) strongly acidic cation exchange resin is Fe3+>Al3 +>Ra2+>Pb2+>Sr2+>Ca2+>Ni2+>Cd2+>Cu2+>Co2+>Zn2+>Mg2+>Ba2+>K+>NH4+>Na+>Li+It was found by sampling the ammonium tungstate solution during production that the major impurity ions are present as cationic impurities, such as Fe3+、Sb2+、Pb2+And the impurity ions are precipitated into the APT product in the subsequent evaporation and crystallization process with high probability to cause the APT pollution of the product, and the 001 x 7 resin has strong adsorption capacity to the cation impurities, and combines the durability and the current market price of the resin, and the use condition is low, the pretreatment operation is simple and easy to operate, so the 001 x 7(Na type) strong acid cation exchange resin is preferably used as the resin in the exchange area.
According to the method for purifying the ammonium tungstate solution, the ammonium tungstate solution enters the equipment body through an ammonium tungstate solution inlet located in a feeding area of the equipment body, and sequentially passes through an adsorption area filled with activated carbon and an exchange area filled with resin under the action of gravity and a first distribution plate, a second distribution plate and a third distribution plate, the ammonium tungstate solution can fully soak the activated carbon in the adsorption area under the action of the first distribution plate and the second distribution plate, the activated carbon adsorbs impurities in the ammonium tungstate solution, then the ammonium tungstate solution subjected to impurity adsorption by the activated carbon enters the exchange area under the action of gravity and the second distribution plate and the third distribution plate, the resin in the exchange area is fully soaked, and the resin achieves the purpose of purifying the ammonium tungstate solution by adsorbing the impurities in the ammonium tungstate solution. After activated carbon adsorption and resin exchange impurity removal, the purified ammonium tungstate solution with the tungsten-molybdenum ratio of more than 50000 can be obtained, high-purity APT products with the purity of more than 99.999 percent can be produced and far exceed APT international zero-order product standards, and because the ammonium tungstate solution is in a closed environment in the whole process and does not contact external pollution, the phenomena that impurities of subsequent APT products exceed standards or black spots occur can be effectively avoided, the loss of production enterprises caused by the fact that the impurities of APT exceed standards is avoided, meanwhile, the whole equipment is simple and convenient to operate, low in investment cost and remarkable in economic benefit.
According to an embodiment of the present invention, referring to fig. 6, the method for purifying an ammonium tungstate solution further includes, after the activated carbon and the resin are saturated by adsorption:
s200: supplying pure water through an ammonium tungstate solution inlet to carry out desorption treatment on the activated carbon and the resin so as to obtain desorption liquid, and discharging the desorption liquid through an ammonium tungstate solution outlet after the desorption liquid is purified
In the step, pure water is supplied through an ammonium tungstate solution inlet to carry out desorption treatment on the activated carbon and the resin so as to obtain desorption liquid, and the desorption liquid is discharged through an ammonium tungstate solution outlet after being purified. Therefore, the regeneration of the activated carbon and the resin can be realized, the recycling of the activated carbon and the resin is realized, and the input cost of the process is obviously reduced.
Specifically, before the ammonium tungstate solution is sent to the ammonium tungstate solution purification equipment, ion exchange separation, adsorption and impurity removal are carried out on the ammonium tungstate solution by using 201 × 7 (Cl-type) strongly basic anion exchange resin in advance to obtain a primary molybdenum-ammonium tungstate removal solution with a tungsten-molybdenum ratio of about 12500; and then the primary molybdenum-ammonium tungstate-removing solution is sent to a feeding area from an ammonium tungstate solution inlet of the feeding area of the equipment body, the primary molybdenum-ammonium tungstate-removing solution is distributed to an activated carbon adsorption area through a first distribution plate, fine solid particle impurities and part of ionic impurities existing in a molybdenum polymerization anion state are adsorbed and removed by activated carbon, and then the primary molybdenum-ammonium tungstate-removing solution is distributed to a resin exchange area through a second distribution plate, wherein cationic impurities such As lead (Pb), tin (Sn), antimony (Sb), arsenic (As) and the like are removed by resin exchange adsorption, and the cationic impurities enter a discharging area through a third distribution plate and are discharged from a purified ammonium tungstate solution outlet of the discharging area to obtain a purified ammonium tungstate solution with a tungsten-molybdenum ratio of more than 50000 for producing an APT product through subsequent evaporative crystallization, so that a high-purity APT product with a purity of more than 99.999% can be obtained. The gas produced during the purification is discharged from the gas outlet of the feed zone. Along with the quantity increase of equipment processing ammonium tungstate solution, the active carbon in adsorption zone and the resin in exchange area are because of the constantly increase of impurity adsorption's volume, when being close to saturation, active carbon and resin deactivation, accessible ammonium tungstate solution entry is injected high pure water desorption active carbon and resin into the equipment body this moment, and the desorption liquid that obtains is retrieved, reciprocates many times until active carbon and resin regeneration, from this, realizes the cyclic utilization of active carbon and resin, and the input cost of showing reduction equipment.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (4)
1. An apparatus for purifying an ammonium tungstate solution, comprising:
the equipment comprises an equipment body, wherein a feeding area, an adsorption area, an exchange area and a discharging area are defined in the equipment body from top to bottom, the adsorption area is filled with activated carbon, and the exchange area is filled with resin;
a first distribution plate disposed between the feed zone and the activated carbon adsorption zone;
the second distribution plate is arranged between the activated carbon adsorption area and the resin exchange area;
the third distribution plate is arranged between the resin exchange area and the discharging area;
an ammonium tungstate solution inlet, which is arranged in the feeding area;
an exhaust port disposed in the feed zone;
an outlet of the purified ammonium tungstate solution, which is arranged in the discharging area,
wherein the filling amount of the activated carbon in the adsorption zone is 80-85% of the volume of the adsorption zone, the filling amount of the resin in the exchange zone is 80-85% of the volume of the exchange zone, and the height ratio of the adsorption zone to the exchange zone is 1: 1-1: 2,
the first distribution plate, the second distribution plate and the third distribution plate are water cap distribution plates respectively and independently,
the water cap distribution plate includes:
the water cap distribution plate is provided with a plurality of water cap mounting holes;
the water cap comprises a cap body and a screw rod, one end of the screw rod is connected with the bottom of the cap body, a slit is arranged on the cap body, the other end of the screw rod is matched with the water cap mounting hole through a nut,
the resin is a 001X 7 Na type strong-acid cation exchange resin.
2. The apparatus of claim 1, wherein a flow meter is arranged at the purified ammonium tungstate solution outlet.
3. A method of purifying an ammonium tungstate solution using the apparatus of claim 1 or 2, wherein the method includes:
and feeding ammonium tungstate solution to the feeding area from an ammonium tungstate solution inlet, so that the ammonium tungstate solution sequentially passes through the activated carbon in the adsorption area and the resin in the exchange area to be soaked and adsorbed, so that purified ammonium tungstate solution is obtained, and the purified ammonium tungstate solution is discharged through a purified ammonium tungstate solution outlet.
4. The method of claim 3, wherein after the activated carbon and the resin are saturated by adsorption, the method further comprises:
and supplying pure water through the ammonium tungstate solution inlet to carry out desorption treatment on the activated carbon and the resin so as to obtain desorption liquid, and discharging the desorption liquid through the purified ammonium tungstate solution outlet.
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