CN103103359B - Method for regenerating APT (ammonium paratungstate) by use of APT waste low-grade tungsten slag - Google Patents
Method for regenerating APT (ammonium paratungstate) by use of APT waste low-grade tungsten slag Download PDFInfo
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- CN103103359B CN103103359B CN201210479921.1A CN201210479921A CN103103359B CN 103103359 B CN103103359 B CN 103103359B CN 201210479921 A CN201210479921 A CN 201210479921A CN 103103359 B CN103103359 B CN 103103359B
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- ammonium paratungstate
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 67
- 239000010937 tungsten Substances 0.000 title claims abstract description 67
- 239000002893 slag Substances 0.000 title claims abstract description 46
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title abstract description 14
- 230000001172 regenerating effect Effects 0.000 title abstract 3
- 239000012535 impurity Substances 0.000 claims abstract description 31
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 238000005516 engineering process Methods 0.000 claims abstract description 15
- 238000001238 wet grinding Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 63
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 28
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- 238000010790 dilution Methods 0.000 claims description 10
- 239000012895 dilution Substances 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000003082 abrasive agent Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000003957 anion exchange resin Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 8
- 239000012141 concentrate Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of tungsten resource recycling, and particularly relates to a method for regenerating APT (ammonium paratungstate) by the use of waste low-grade tungsten slag in an APT production process. The invention discloses a method for regenerating APT by use of APT waste low-grade tungsten slag, which is realized by improving the technological parameters of the traditional soda sintering method and comprises the following steps of: (a) grinding and dosing; (b) slag calcining; (c) wet grinding and filtering; (d) two-secondary ion exchange and impurity removal; and (e) evaporating and crystallizing to generate APT. The method provided by the invention can reduce resource waste, improve the utilization rate of resources, and can increase the economic benefits of an enterprise by recycling the APT waste low-grade tungsten slag; the method is suitable for treating the waste low-grade tungsten slag of which the WO3 grade is 2-10%, overcomes the shortcomings of the technology matching the waste and the tungsten concentrate raw material, and can effectively improve the recovery rate of tungsten and reduce environmental pollution; and through the invention, the service life of the tungsten resource of the country can be prolonged, the current situation of shortage in tungsten resource is relieved, the emission of waste can be effectively reduced, and environmental pollution is reduced.
Description
Technical field
The invention belongs to tungsten resource recycling field, be specifically related to one and utilize APT(ammonium paratungstate) method of the useless low tungsten slag regeneration APT that produces in production process.
Background technology
Tungsten ore is one of Dominant Mineral Resources of China; due to blind expansion, the unauthorized and excessive mining of tungsten enterprise and the emerging in multitude of newly-built tungsten smelting enterprise of tungsten industry; cause the gopher of tungsten ore resource, China's tungsten ore resource advantage is progressively disappeared, crisis of resource highlights.Along with the tungsten resource difficult choosing that becomes increasingly complex, all kinds of high impurity, low grade wolfram will become the main raw material sources of tungsten smelting enterprise from now at present.
Ammonium paratungstate is generally used for production tungsten, and tungsten is applied to the departments such as metallurgy, chemical industry, electric and aerospace with pure metal, alloy and compound state, and the tungsten of about half tungsten concentrate is for special steel, and tungsten plays an important role in the development of the national economy.
Through retrieval, there is document to propose the method for two-stage autoclave art breading waste tungsten residue, the rate of recovery of tungsten is reached more than 97%, two-stage autoclave technique all adopts base decomposing technology design for black, white tungsten fine ore and mixing ore deposit.The shortcoming of the method is that its alkali is seriously excessive, must combine to press in conjunction with black, white tungsten fine ore and boil art breading digestion excess base, otherwise high cost.
Through retrieval, have document proposed a kind of from ammonium paratungstate production process, produce containing extracting in tungsten slag and separating tungsten and obtain qualified APT product and containing the method for molybdenum slag, specifically by after sulfuration in ammonium paratungstate production process containing tungsten slag, be immersed in ammonia soln, in crystallizing pan, pass into water vapour and keep pressure 0.1-0.2MPa, cooling by Plate Filtration after reaction, directly enter truck for vulcanlzing pan and remove molybdenum, obtain qualified APT product and molybdenum slag.The shortcoming of the method is also to need to increase the other equipment crystallizing pan with pressure, has increased facility investment.
At present, the useless low tungsten slag producing in domestic APT production technique, mainly to sell other resource returned enterprises with the form of byproduct, carry out the recovery of the micro-metalss such as other copper, tin, zinc, this has wasted tungsten resource to a great extent, or waste residue is turned back to ball-milling technology again, with the tungsten concentrate processing of arranging in pairs or groups, the shortcoming of this technique is in waste residue, to have a large amount of impurity elements, operation impact on postorder is larger, very high to the job requirements of removal of impurities operation, affect the stability of processing parameter, and can produce larger pollution to environment.
Summary of the invention
The object of the invention is for the defect existing in background technology, propose the method for the useless low tungsten slag regeneration APT producing in a kind of APT of utilization production process, by improving the processing parameter of traditional soda sintered method, make it be suitable for processing WO
3the useless low tungsten slag charge of grade within the scope of 2-10%, and overcome waste material and the tungsten concentrate existing defect for the treatment of process of arranging in pairs or groups, reach the rate of recovery that improves tungsten, reduce costs and reduce the object of environmental pollution.
In order to reach above object, the present invention adopts following technical scheme:
A method of utilizing the useless low tungsten slag regeneration of APT APT, its step is as follows:
A. abrasive material and batching: useless APT low tungsten sizing is arrived to-125 order>=90%, in order to prevent material melting freezing of a furnace in calcination process, WO in useless low tungsten slag charge
3grade be formulated to 4-8%, prepare burden afterwards, the add-on (by weight calculate) of batching middle soda is WO
3the 135-145% of theoretical amount, the add-on of nitre in batching (calculating by weight) is WO
3the 2.0-2.8% of theoretical amount;
B. slag charge calcining: the slag charge preparing in step a is calcined, generated sintered material;
C. wet-milling and filtration: sintered material is added to softening water wet-milling, and liquid-solid ratio is 1.70:1-1.85:1, and the slip grinding boils 1.6-2h by steam indirect heating, and sodium wolframate is stripping from sintered material, filters, and obtains WO
3concentration is the coarse sodium tungstate of 20-30g/L;
D. two secondary ion exchange removal of impurities: exchange for the first time removal of impurities, by WO in step c coarse sodium tungstate
3concentration dilution below 30g/L, after exchange resin is saturated, make eluent with the NaOH solution of concentration 25g/L, exchange resin is carried out to 1-2 drip washing, carry out desorb with the NaOH solution of 40g/L again, the sodium tungstate solution of desorb gained, pH value is greater than 9, now carry out evaporation concentration by traditional technology, sodium wolframate percent crystallization in massecuite is controlled at 60%-70%, obtains sodium wolframate crystallization, after filtering, dissolve with the pure water that liquid-solid ratio is 1.5:1-2.0:1, solution carries out ion-exchange removal of impurities for the second time more afterwards; Exchange for the second time removal of impurities, by WO
3concentration dilution below 20g/L, after exchange resin is saturated, with the NH of concentration 10g/L
4cl solution is made eluent, carries out exchange resin drip washing, then uses the NH of 20-30g/L
4cl solution is made strippant, carries out desorb, obtains (NH
4)
2wO
4solution, controls its pH value and is greater than 9;
E. evaporative crystallization produces pure APT: exchanging for the second time (the NH that removal of impurities obtains in steps d
4)
2wO
4solution, carries out evaporation concentration by traditional technology, is heated with stirring to boiling and makes ammonia volatilization, and in the time that solution pH value is down to 7.0-7.7, APT separates out, as (NH
4)
2wO
4solution density is 1.06-1.12g/m
3time, stopping heating, cooling 0.5h, drains into vacuumfilter by cooled solution and carries out filtration washing, and APT percent crystallization in massecuite is controlled at below 70% and obtains wet APT, dry at 90-120 ℃ of temperature, after the mixing of sieving, is packaged to be APT finished product.
As the preferred embodiment of the present invention, in step b, the slag charge preparing in step a to be calcined in rotary kiln, its burning zone temperature is 1000-1350 ℃, the rotating speed of rotary kiln is 0.3-1.3r/min, and the temperature of kiln tail smoke-box is that 800-950 ℃, pressure are-110--190Pa; The temperature out of preheater is that 230-280 ℃, inlet pressure are that-120--200Pa, top hole pressure are-7000--7500Pa; The temperature of kiln head cover is 700-800 ℃, and calcination time is 1.6-2.5h, has calcined rear generation sintered material.
As the preferred embodiment of the present invention, in step c, sintered material is first added to softening water wet-milling through rod mill, the slip grinding flows in steel basin and boils 1.7h by steam indirect heating, sodium wolframate is stripping from sintered material, then filter with drum vacuumfilter or plate-and-frame filter press, obtain coarse sodium tungstate.
As the preferred embodiment of the present invention, in steps d, what two secondary ion exchange removal of impurities adopted is 201 × 7 type Strong basic anion exchange resins.
As the preferred embodiment of the present invention, in step a, by useless APT low tungsten sizing, to-125 order>=90%, in useless low tungsten slag charge, the grade of WO3 will be formulated to 6%, and soda add-on is WO
3140% of theoretical amount, nitre add-on is WO
32.1% of theoretical amount; In step b, the slag charge preparing in step a to be calcined in rotary kiln, its burning zone temperature is 1100-1250 ℃, and the rotating speed of rotary kiln is 0.9r/min, and the temperature of kiln tail smoke-box is that 850-900 ℃, pressure are-150--180Pa; The temperature out of preheater is that 245-270 ℃, inlet pressure are that-140--190Pa, top hole pressure are-7100--7300Pa; The temperature of kiln head cover is 750-780 ℃; Calcination time is 1.8h; In step c, sintered material is added to softening water wet-milling, liquid-solid ratio is 1.76:1, and the slip grinding boils 1.7h by steam indirect heating, and sodium wolframate is stripping from sintered material, then filters, and obtains WO
3concentration is the coarse sodium tungstate of 28g/L; In steps d, sodium wolframate percent crystallization in massecuite is controlled at 65%, obtains sodium wolframate crystallization, after filtering, dissolves with the pure water that liquid-solid ratio is 1.7:1; With the NH of 25g/L
4cl solution is made strippant, carries out desorb, obtains (NH
4)
2wO
4solution; In step e, in the time that solution pH value is down to 7.3, APT separates out, as (NH
4)
2wO
4solution density is 1.08g/m
3time, stopping heating, cooling 0.5h, drains into vacuumfilter by material and carries out filtration washing, and APT percent crystallization in massecuite is controlled at below 70%, after the wet APT obtaining is dry at 100 ℃ of temperature, after the mixing of sieving, is packaged to be APT finished product.
The invention has the beneficial effects as follows: 1. the present invention can realize the useless low tungsten slag regeneration of APT APT, effectively reduces the wasting of resources, improves the utilization ratio of resource; 2. by the recycling to the useless low tungsten slag of APT, can improve the economic benefit of enterprise; 3. method of the present invention, by changing the processing parameter in traditional APT production process, realizes the object of the useless low tungsten slag regeneration of APT APT, has effectively utilized the existing installation of enterprise, and not needing additionally increases equipment, thereby has effectively reduced cost; 4. by improving the processing parameter of traditional soda sintered method, method of the present invention is suitable for processing WO
3the useless low tungsten slag charge of grade within the scope of 2-10%, and overcome waste material and the tungsten concentrate raw material existing defect for the treatment of process of arranging in pairs or groups, can effectively improve the rate of recovery of tungsten, reduce environmental pollution; 5. by enforcement of the present invention, can extend the working life of China's tungsten resource, alleviate the short present situation of tungsten resource supply; 6. by enforcement of the present invention, can effectively reduce the discharge of waste, reduce environmental pollution.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
embodiment 1:
A. abrasive material and batching: useless APT low tungsten sizing, to-125 order>=90%, is got to WO
3grade is formulated to 4% useless low tungsten slag charge 100kg, prepares burden afterwards, and the add-on of batching middle soda is 5.4kg, and in batching, the add-on of nitre amount is 0.08kg;
B. slag charge calcining: the slag charge preparing in step a is calcined in rotary kiln, and its burning zone temperature is 1000-1100 ℃, and the rotating speed of rotary kiln is 0.3r/min, the temperature of kiln tail smoke-box is that 800-850 ℃, pressure are-110--150Pa; The temperature out of preheater is that 230-245 ℃, inlet pressure are that-120--160Pa, top hole pressure are-7000--7100Pa; The temperature of kiln head cover is 700-750 ℃; Calcination time is 1.6h, has calcined rear generation sintered material;
C. wet-milling and filtration: sintered material is added to softening water wet-milling, and liquid-solid ratio is 1.70:1, and the slip grinding boils 1.6h by steam indirect heating, and sodium wolframate is stripping from sintered material, filters, and obtains WO
3concentration is the coarse sodium tungstate of 20g/L;
D. two secondary ion exchange removal of impurities: exchange for the first time removal of impurities, by WO in step c coarse sodium tungstate
3concentration dilution below 30g/L, after exchange resin is saturated, make eluent with the NaOH solution of concentration 25g/L, exchange resin is carried out to 1-2 drip washing, carry out desorb with the NaOH solution of 40g/L again, the sodium tungstate solution of desorb gained, pH value is greater than 9, now carry out evaporation concentration by traditional technology, sodium wolframate percent crystallization in massecuite is controlled at 60%, obtains sodium wolframate crystallization, after filtering, dissolve with the pure water that liquid-solid ratio is 1.5:1, solution carries out ion-exchange removal of impurities for the second time more afterwards; Exchange for the second time removal of impurities, by WO
3concentration dilution below 20g/L, after exchange resin is saturated, with the NH of concentration 10g/L
4cl solution is made eluent, carries out exchange resin drip washing, then uses the NH of 20g/L
4cl solution is made strippant, carries out desorb, obtains (NH
4)
2wO
4solution, controls its pH value and is greater than 9;
E. evaporative crystallization produces pure APT: exchanging for the second time (the NH that removal of impurities obtains in steps d
4)
2wO
4solution, carries out evaporation concentration by traditional technology, is heated with stirring to boiling and makes ammonia volatilization, and in the time that solution pH value is down to 7.0, APT separates out, as (NH
4)
2wO
4solution density is 1.06g/m
3time, stop heating, cooling 0.5h, cooled solution is drained into vacuumfilter and carry out filtration washing, APT percent crystallization in massecuite is controlled at below 70% and obtains wet APT, dry at 90 ℃ of temperature, sieve mix after be packaged to be APT finished product, the weight of the APT finished product obtaining is 3.808kg.
In the present embodiment, WO
3the rate of recovery reach 95.2%.
embodiment 2:
A. abrasive material and batching: useless APT low tungsten sizing, to-125 order>=90%, is got to WO
3grade is formulated to 8% useless low tungsten slag charge 100kg, prepares burden afterwards, and the add-on of batching middle soda is 11.6kg, and in batching, the add-on of nitre is 0.224kg;
B. slag charge calcining: the slag charge preparing in step a is calcined in rotary kiln, and its burning zone temperature is 1250-1350 ℃, and the rotating speed of rotary kiln is 1.3r/min, the temperature of kiln tail smoke-box is that 900-950 ℃, pressure are-180--190Pa; The temperature out of preheater is 270-280 ℃, inlet pressure :-190--200Pa, top hole pressure :-7300--7500Pa; The temperature of kiln head cover is 780-800 ℃; Calcination time is 2.5h, has calcined rear generation sintered material;
C. wet-milling and filtration: sintered material is added to softening water wet-milling, and liquid-solid ratio is 1.85:1, and the slip grinding boils 2h by steam indirect heating, and sodium wolframate is stripping from sintered material, filters, and obtains WO
3concentration is the coarse sodium tungstate of 30g/L;
D. two secondary ion exchange removal of impurities: exchange for the first time removal of impurities, by WO in step c coarse sodium tungstate
3concentration dilution below 30g/L, after exchange resin is saturated, make eluent with the NaOH solution of concentration 25g/L, exchange resin is carried out to 1-2 drip washing, carry out desorb with the NaOH solution of 40g/L again, the sodium tungstate solution of desorb gained, pH value is greater than 9, now carry out evaporation concentration by traditional technology, sodium wolframate percent crystallization in massecuite is controlled at 70%, obtains sodium wolframate crystallization, after filtering, dissolve with the pure water that liquid-solid ratio is 2.0:1, solution carries out ion-exchange removal of impurities for the second time more afterwards; Exchange for the second time removal of impurities, by WO
3concentration dilution below 20g/L, after exchange resin is saturated, with the NH of concentration 10g/L
4cl solution is made eluent, carries out exchange resin drip washing, then uses the NH of 30g/L
4cl solution is made strippant, carries out desorb, obtains (NH
4)
2wO
4solution, controls its pH value and is greater than 9;
E. evaporative crystallization produces pure APT: exchanging for the second time (the NH that removal of impurities obtains in steps d
4)
2wO
4solution, carries out evaporation concentration by traditional technology, is heated with stirring to boiling and makes ammonia volatilization, and in the time that solution pH value is down to 7.7, APT separates out, as (NH
4)
2wO
4solution density is 1.12g/m
3time, stop heating, cooling 0.5h, cooled solution is drained into vacuumfilter and carry out filtration washing, APT percent crystallization in massecuite is controlled at below 70% and obtains wet APT, dry at 120 ℃ of temperature, sieve mix after be packaged to be APT finished product, the weight of the APT finished product obtaining is 7.736kg.
In the present embodiment, WO
3the rate of recovery reach 96.7%.
embodiment 3:
A. abrasive material and batching: useless APT low tungsten sizing, to-125 order>=90%, is got to WO
3grade is formulated to 6% useless low tungsten slag charge 100kg, prepares burden afterwards, and the add-on of batching middle soda is 8.4kg, and in batching, the add-on of nitre is 0.126kg;
B. slag charge calcining: the slag charge preparing in step a is calcined in rotary kiln, and its burning zone temperature is 1100-1250 ℃, and the rotating speed of rotary kiln is 0.9r/min, the temperature of kiln tail smoke-box is that 850-900 ℃, pressure are-150--180Pa; The temperature out of preheater is that 245-270 ℃, inlet pressure are that-140--190Pa, top hole pressure are-7100--7300Pa; The temperature of kiln head cover is 750-780 ℃; Calcination time is 1.8h, has calcined rear generation sintered material;
C. wet-milling and filtration: sintered material is added to softening water wet-milling, and liquid-solid ratio is 1.76:1, and the slip grinding boils 1.7h by steam indirect heating, and sodium wolframate is stripping from sintered material, filters, and obtains WO
3concentration is the coarse sodium tungstate of 28g/L;
D. two secondary ion exchange removal of impurities: exchange for the first time removal of impurities, by WO in step c coarse sodium tungstate
3concentration dilution below 30g/L, after exchange resin is saturated, make eluent with the NaOH solution of concentration 25g/L, exchange resin is carried out to 1-2 drip washing, carry out desorb with the NaOH solution of 40g/L again, the sodium tungstate solution of desorb gained, pH value is greater than 9, now carry out evaporation concentration by traditional technology, sodium wolframate percent crystallization in massecuite is controlled at 65%, obtains sodium wolframate crystallization, after filtering, dissolve with the pure water that liquid-solid ratio is 1.7:1, solution carries out ion-exchange removal of impurities for the second time more afterwards; Exchange for the second time removal of impurities, by WO
3concentration dilution below 20g/L, after exchange resin is saturated, with the NH of concentration 10g/L
4cl solution is made eluent, carries out exchange resin drip washing, then uses the NH of 25g/L
4cl solution is made strippant, carries out desorb, obtains (NH
4)
2wO
4solution, controls its pH value and is greater than 9;
E. evaporative crystallization produces pure APT: exchanging for the second time (the NH that removal of impurities obtains in steps d
4)
2wO
4solution, carries out evaporation concentration by traditional technology, is heated with stirring to boiling and makes ammonia volatilization, and in the time that solution pH value is down to 7.3, APT separates out, as (NH
4)
2wO
4solution density is 1.08g/m
3time, stop heating, cooling 0.5h, cooled solution is drained into vacuumfilter and carry out filtration washing, APT percent crystallization in massecuite is controlled at below 70% and obtains wet APT, dry at 100 ℃ of temperature, sieve mix after be packaged to be APT finished product, the weight of the APT finished product obtaining is 5.676kg.
In the present embodiment, WO
3the rate of recovery reach 94.6%.
The above embodiment has only expressed the preferred embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion, improvement and substitute, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (5)
1. a method of utilizing the useless low tungsten slag regeneration of ammonium paratungstate ammonium paratungstate, is characterized in that: its step is as follows:
A. abrasive material and batching: useless ammonium paratungstate low tungsten sizing is arrived to-125 order>=90%, WO in useless low tungsten slag charge
3grade be formulated to 4-8%, prepare burden afterwards, batching middle soda add-on be WO
3the 135-145% of theoretical amount, in batching, the add-on of nitre is WO
3the 2.0-2.8% of theoretical amount;
B. slag charge calcining: the slag charge preparing in step a is calcined, generated sintered material;
C. wet-milling and filtration: sintered material is added to softening water wet-milling, and liquid-solid ratio is 1.70:1-1.85:1, and the slip grinding boils 1.6-2h by steam indirect heating, and sodium wolframate is stripping from sintered material, filters, and obtains WO
3concentration is the coarse sodium tungstate of 20-30g/L;
D. two secondary ion exchange removal of impurities: exchange for the first time removal of impurities, by WO in step c coarse sodium tungstate
3concentration dilution below 30g/L, after exchange resin is saturated, make eluent with the NaOH solution of concentration 25g/L, exchange resin is carried out to 1-2 drip washing, carry out desorb with the NaOH solution of 40g/L again, the sodium tungstate solution of desorb gained, pH value is greater than 9, now carry out evaporation concentration by traditional technology, sodium wolframate percent crystallization in massecuite is controlled at 60%-70%, obtains sodium wolframate crystallization, after filtering, dissolve with the pure water that liquid-solid ratio is 1.5:1-2.0:1, solution carries out ion-exchange removal of impurities for the second time more afterwards; Exchange for the second time removal of impurities, by WO
3concentration dilution below 20g/L, after exchange resin is saturated, with the NH of concentration 10g/L
4cl solution is made eluent, carries out exchange resin drip washing, then uses the NH of 20-30g/L
4cl solution is made strippant, carries out desorb, obtains (NH
4)
2wO
4solution, controls its pH value and is greater than 9;
E. evaporative crystallization produces pure ammonium paratungstate: exchanging for the second time (the NH that removal of impurities obtains in steps d
4)
2wO
4solution, carries out evaporation concentration by traditional technology, is heated with stirring to boiling and makes ammonia volatilization, and in the time that solution pH value is down to 7.0-7.7, ammonium paratungstate is separated out, as (NH
4)
2wO
4solution density is 1.06-1.12g/m
3time, stop heating, cooling 0.5h, cooled solution is drained into vacuumfilter and carry out filtration washing, ammonium para-tungstate crystal rate is controlled at below 70% and obtains wet ammonium paratungstate, dry at 90-120 ℃ of temperature, after the mixing of sieving, is packaged to be ammonium paratungstate finished product.
2. a kind of method of utilizing the useless low tungsten slag regeneration of ammonium paratungstate ammonium paratungstate according to claim 1, it is characterized in that: in step b, the slag charge preparing in step a is calcined in rotary kiln, its burning zone temperature is 1000-1350 ℃, the rotating speed of rotary kiln is 0.3-1.3r/min, and the temperature of kiln tail smoke-box is that 800-950 ℃, pressure are-110--190Pa; The temperature out of preheater is that 230-280 ℃, inlet pressure are that-120--200Pa, top hole pressure are-7000--7500Pa; The temperature of kiln head cover is 700-800 ℃, and calcination time is 1.6-2.5h, has calcined rear generation sintered material.
3. a kind of method of utilizing the useless low tungsten slag regeneration of ammonium paratungstate ammonium paratungstate according to claim 1, it is characterized in that: in step c, sintered material is first added to softening water wet-milling through rod mill, the slip grinding flows in steel basin and boils 1.7h by steam indirect heating, sodium wolframate is stripping from sintered material, then filter with drum vacuumfilter or plate-and-frame filter press, obtain coarse sodium tungstate.
4. a kind of method of utilizing the useless low tungsten slag regeneration of ammonium paratungstate ammonium paratungstate according to claim 1, is characterized in that: in steps d, what two secondary ion exchange removal of impurities adopted is 201 × 7 type Strong basic anion exchange resins.
5. a kind of method of utilizing the useless low tungsten slag regeneration of ammonium paratungstate ammonium paratungstate according to claim 1, is characterized in that: in step a, useless ammonium paratungstate low tungsten sizing is arrived to-125 order>=90%, WO in useless low tungsten slag charge
3grade to be formulated to 6%, soda add-on is WO
3140% of theoretical amount, nitre add-on is WO
32.1% of theoretical amount; In step b, the slag charge preparing in step a to be calcined in rotary kiln, its burning zone temperature is 1100-1250 ℃, and the rotating speed of rotary kiln is 0.9r/min, and the temperature of kiln tail smoke-box is that 850-900 ℃, pressure are-150--180Pa; The temperature out of preheater is that 245-270 ℃, inlet pressure are that-140--190Pa, top hole pressure are-7100--7300Pa; The temperature of kiln head cover is 750-780 ℃; Calcination time is 1.8h; In step c, sintered material is added to softening water wet-milling, liquid-solid ratio is 1.76:1, and the slip grinding boils 1.7h by steam indirect heating, and sodium wolframate is stripping from sintered material, then filters, and obtains WO
3concentration is the coarse sodium tungstate of 28g/L; In steps d, sodium wolframate percent crystallization in massecuite is controlled at 65%, obtains sodium wolframate crystallization, after filtering, dissolves with the pure water that liquid-solid ratio is 1.7:1; With the NH of 25g/L
4cl solution is made strippant, carries out desorb, obtains (NH
4)
2wO
4solution; In step e, in the time that solution pH value is down to 7.3, ammonium paratungstate is separated out, as (NH
4)
2wO
4solution density is 1.08g/m
3time, stopping heating, cooling 0.5h, drains into vacuumfilter by material and carries out filtration washing, and ammonium para-tungstate crystal rate is controlled at below 70%, after the wet ammonium paratungstate obtaining is dry at 100 ℃ of temperature, after the mixing of sieving, is packaged to be ammonium paratungstate finished product.
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| CN103523800B (en) * | 2013-09-24 | 2015-01-07 | 中国有色集团（广西）平桂飞碟股份有限公司 | Method for recovering excess sodium hydroxide in tungsten smelting crude sodium tungstate solution |
| CN104046800B (en) * | 2014-07-11 | 2016-01-20 | 谭春波 | A kind of from containing the technique extracting white tungsten fine ore ferberite or tungstenic waste residue |
| CN104263975B (en) * | 2014-10-09 | 2016-09-14 | 江西稀有金属钨业控股集团有限公司 | There is the tungsten mineral material metallurgical technology of multiple closed loop |
| CN104263972B (en) * | 2014-10-09 | 2016-03-16 | 中南大学 | There is the tungsten mineral material metallurgical system of multiple closed loop |
| CN104263976B (en) * | 2014-10-09 | 2016-07-27 | 江西稀有金属钨业控股集团有限公司 | The tungsten mineral material metallurgical technology of omnidistance non-pollution discharge |
| CN104263971B (en) * | 2014-10-09 | 2016-08-24 | 中南大学 | The system of APT is prepared by tungsten mineral material no pollution |
| CN104263973B (en) * | 2014-10-09 | 2016-09-14 | 江西稀有金属钨业控股集团有限公司 | The method being prepared APT by the many closed loops of tungsten mineral material |
| CN104263974B (en) * | 2014-10-09 | 2016-09-07 | 江西稀有金属钨业控股集团有限公司 | The method being prepared APT by tungsten mineral material no effuent discharge |
| CN104630490B (en) * | 2015-02-10 | 2017-01-11 | 江西稀有金属钨业控股集团有限公司 | Method for preparing ammonium tungstate |
| CN106191455A (en) * | 2016-07-08 | 2016-12-07 | 大余县东宏锡制品有限公司 | A kind of tungsten essence artware preparation method refined from ammonium paratungstate solid slag |
| CN106011483A (en) * | 2016-07-08 | 2016-10-12 | 大余县东宏锡制品有限公司 | Preparing method for fine artwork of tin extracted from ammonium paratungstate solid waste residues |
| CN106435224B (en) * | 2016-08-17 | 2019-01-25 | 湖南金源新材料股份有限公司 | The method for preparing ammonium paratungstate with tungsten waste |
| CN106379941B (en) * | 2016-10-12 | 2017-08-04 | 佛山迅拓奥科技有限公司 | A kind of preparation method of high-purity tungstic acid |
| CN106673064A (en) * | 2016-12-05 | 2017-05-17 | 荆门德威格林美钨资源循环利用有限公司 | Method for producing ammonium paratungstate |
| CN107746966A (en) * | 2017-09-29 | 2018-03-02 | 湖南行者环保科技有限公司 | A kind of method that joint disposal ammonium paratungstate slag charge reclaims micro rare metal |
| CN109796046A (en) * | 2019-03-20 | 2019-05-24 | 江西省鑫盛钨业有限公司 | A kind of preparation process of high-purity ammonium paratungstate |
| CN109943735A (en) * | 2019-03-23 | 2019-06-28 | 江西省鑫盛钨业有限公司 | A kind of technique preparing ammonium paratungstate with tungsten waste |
| CN110343857B (en) * | 2019-07-15 | 2021-03-23 | 厦门钨业股份有限公司 | Method for treating tungsten ore |
| CN110735052B (en) * | 2019-10-16 | 2021-08-24 | 清远市恒德环保科技有限公司 | Method for enriching tungsten in low-grade APT slag |
| CN111217394B (en) * | 2020-02-18 | 2022-04-29 | 厦门钨业股份有限公司 | high-Fischer low-apparent-density ammonium paratungstate and production method and equipment thereof |
| CN112678871B (en) * | 2021-01-29 | 2022-10-28 | 宁波江丰电子材料股份有限公司 | Preparation method of ultra-pure ammonium paratungstate |
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| US4303622A (en) * | 1981-01-19 | 1981-12-01 | Amax Inc. | Chemical treatment of low-grade wolframite concentrate having high Mo/WO3 ratio |
| FR2630723B1 (en) * | 1988-04-29 | 1990-07-13 | Atochem | PROCESS FOR THE PREPARATION OF FERRIC CHLORIDE FROM DILUTED HYDROCHLORIC ACID |
| CN1377980A (en) * | 2002-02-06 | 2002-11-06 | 王旭升 | Process for preparing high purity ammonium para-tungstate using hihg-molybdenum tungsten ore |
| CN101333598B (en) * | 2008-01-17 | 2010-07-21 | 郴州钻石钨制品有限责任公司 | Method for separating and extracting metallic tungsten and molybdenum from molybdenum removal slag generated by smelting tungsten |
| CN101565778B (en) * | 2009-05-22 | 2011-02-09 | 中南大学 | Method for depositing and separating tungsten and molybdenum in tungstate/molybdate mixed solution |
| EP2450312A1 (en) * | 2010-11-03 | 2012-05-09 | Montanuniversität Leoben | Recovery of tungsten from waste material by ammonium leaching |
| CN102061524A (en) * | 2010-11-08 | 2011-05-18 | 崇义章源钨业股份有限公司 | Monocrystal ammonium paratungstate and preparation method thereof |
| CN102071313B (en) * | 2011-01-29 | 2012-09-05 | 湖南辰州矿业股份有限公司 | Method for treating tungsten-containing and molybdenum-containing slag produced in ammonium paratungstate production process |
| CN102212697B (en) * | 2011-05-18 | 2013-07-10 | 湖南稀土金属材料研究院 | Tungsten slag treatment method |
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