CN103103359A - 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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- CN103103359A CN103103359A CN2012104799211A CN201210479921A CN103103359A CN 103103359 A CN103103359 A CN 103103359A CN 2012104799211 A CN2012104799211 A CN 2012104799211A CN 201210479921 A CN201210479921 A CN 201210479921A CN 103103359 A CN103103359 A CN 103103359A
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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
- 238000000034 method Methods 0.000 title claims abstract description 31
- 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 abstract description 14
- 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
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 238000005516 engineering process Methods 0.000 claims abstract description 15
- 238000001238 wet grinding Methods 0.000 claims abstract description 15
- 238000005342 ion exchange Methods 0.000 claims abstract description 12
- 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
- 239000000243 solution Substances 0.000 claims description 56
- 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 26
- 230000008025 crystallization Effects 0.000 claims description 26
- 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
- 238000002156 mixing 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
- 238000007873 sieving Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 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
- 238000001035 drying Methods 0.000 claims description 2
- 150000002500 ions Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000012141 concentrate Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 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
- 238000000227 grinding Methods 0.000 abstract 1
- 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
- 230000002950 deficient Effects 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 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
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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 a kind of APT(of utilization 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 the unauthorized and excessive mining of the blind expansion of tungsten industry, tungsten enterprise and emerging in multitude of newly-built tungsten smelting enterprise; 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 for the production of tungsten, and tungsten is applied to the departments such as metallurgy, chemical industry, electric and aerospace with pure metal, alloy and compound state, and approximately the tungsten of half tungsten concentrate is used 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 reclaim of tungsten rate is reached more than 97%, two-stage autoclave technique all adopts the 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 unite to press in conjunction with black, white tungsten fine ore and boil art breading digestion excess base, otherwise high cost.
Through retrieval, there is document to propose extract in the tungsten slag and separate tungsten and obtain qualified APT product and the method that contains the molybdenum slag a kind of containing of producing from the ammonium paratungstate production process, specifically will contain the tungsten slag after the ammonium paratungstate production Sulfur During Process, be immersed in ammonia soln, pass into water vapour and keep pressure 0.1-0.2MPa in crystallizing pan, 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 that produces 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 to have a large amount of impurity elements in waste residue, operation impact on postorder is larger, job requirements to the removal of impurities operation is very high, affects the stability of processing parameter, and can produce larger pollution to environment.
Summary of the invention
The objective of the invention is for the defective that exists in background technology, the method for the useless low tungsten slag regeneration APT that proposes to produce in a kind of APT of utilization production process by improving the processing parameter of traditional soda sintered method, makes it be suitable for processing WO
3The useless low tungsten slag charge of grade in the 2-10% scope, and overcome waste material and the tungsten concentrate existing defective for the treatment of process of arranging in pairs or groups, reach and improve the reclaim of tungsten rate, reduce costs and reduce the purpose of environmental pollution.
In order to reach above purpose, the present invention adopts following technical scheme:
A kind of method of utilizing the useless low tungsten slag regeneration of APT APT, its step is as follows:
A. abrasive material and batching: with the useless low tungsten sizing of APT to-125 orders 〉=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 for preparing in step a is calcined, generated sintered material;
C. wet-milling and filtration: sintered material is added the softening water wet-milling, and liquid-solid ratio is 1.70:1-1.85:1, and the slip that grinds boils 1.6-2h with the 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, with WO in step c coarse sodium tungstate
3Concentration dilution below 30g/L, after exchange resin is saturated, NaOH solution with concentration 25g/L is made eluent, exchange resin is carried out 1-2 drip washing, NaOH solution with 40g/L carries out desorb again, the sodium tungstate solution of desorb gained, the pH value is greater than 9, carry out evaporation concentration by traditional technology this moment, the sodium wolframate percent crystallization in massecuite is controlled at 60%-70%, obtains the sodium wolframate crystallization, after filtering, the pure water that is 1.5:1-2.0:1 with liquid-solid ratio dissolves, and solution carries out ion-exchange removal of impurities for the second time more afterwards; Exchange for the second time removal of impurities, with 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 is controlled its pH value 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 APT separates out when pH is down to 7.0-7.7, as (NH
4)
2WO
4Solution density is 1.06-1.12g/m
3The time, stopped heating, cooling 0.5h drains into vacuumfilter with cooled solution and carries out filtration washing, and the APT percent crystallization in massecuite is controlled at and obtains wet APT below 70%, and is dry at 90-120 ℃ of temperature, sieves to be packaged to be the APT finished product after mixing.
As the preferred embodiment of the present invention, in step b, the slag charge for 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, the temperature of kiln tail smoke-box be 800-950 ℃, pressure be-110--190Pa; The temperature out of preheater be 230-280 ℃, inlet pressure be-120--200Pa, top hole pressure be-7000--7500Pa; The temperature of kiln head cover is 700-800 ℃, and calcination time is 1.6-2.5h, generation sintered material after calcining is completed.
As the preferred embodiment of the present invention, in step c, sintered material is first added the softening water wet-milling through rod mill, the slip that grinds flows in steel basin and boils 1.5-2h with the 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 were adopted is 201 * 7 type Strong basic anion exchange resins.
As the preferred embodiment of the present invention, in step a, to-125 orders 〉=90%, in useless low tungsten slag charge, the grade of WO3 will be formulated to 6% with the useless low tungsten sizing of APT, and the soda add-on is WO
3140% of theoretical amount, nitre add-on are WO
32.1% of theoretical amount; In step b, the slag charge for preparing in step a is calcined in rotary kiln, its burning zone temperature is 1100-1250 ℃, the rotating speed of rotary kiln is 0.9r/min, the temperature of kiln tail smoke-box be 850-900 ℃, pressure be-150--180Pa; The temperature out of preheater be 245-270 ℃, inlet pressure be-140--190Pa, top hole pressure be-7100--7300Pa; The temperature of kiln head cover is 750-780 ℃; Calcination time is 1.8h; In step c, sintered material is added the softening water wet-milling, liquid-solid ratio is 1.76:1, and the slip that grinds boils 1.7h with the 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, the sodium wolframate percent crystallization in massecuite is controlled at 65%, obtains the sodium wolframate crystallization, and after filtering, the pure water that is 1.7:1 with liquid-solid ratio dissolves; NH with 25g/L
4Cl solution is made strippant, carries out desorb, obtains (NH
4)
2WO
4Solution; In step e, APT separates out when pH is down to 7.3, as (NH
4)
2WO
4Solution density is 1.08g/m
3The time, stopped heating, cooling 0.5h drains into vacuumfilter with material and carries out filtration washing, and the APT percent crystallization in massecuite is controlled at below 70%, and the wet APT that obtains is after drying at 100 ℃ of temperature, and sieving is packaged to be the APT finished product after mixing.
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, realize the purpose of the useless low tungsten slag regeneration of APT APT, 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 in the 2-10% scope, and overcome waste material and the tungsten concentrate raw material existing defective for the treatment of process of arranging in pairs or groups, can effectively improve the reclaim of tungsten rate, 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 discharging of waste, environmental contamination reduction.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1:
A. abrasive material and batching: the useless low tungsten sizing of APT to-125 orders 〉=90%, is got 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 for 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 be 800-850 ℃, pressure be-110--150Pa; The temperature out of preheater be 230-245 ℃, inlet pressure be-120--160Pa, top hole pressure be-7000--7100Pa; The temperature of kiln head cover is 700-750 ℃; Calcination time is 1.6h, generation sintered material after calcining is completed;
C. wet-milling and filtration: sintered material is added the softening water wet-milling, and liquid-solid ratio is 1.70:1, and the slip that grinds boils 1.6h with the 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, with 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 1-2 drip washing, NaOH solution with 40g/L carries out desorb again, the sodium tungstate solution of desorb gained, and the pH value is greater than 9, carry out evaporation concentration by traditional technology this moment, the sodium wolframate percent crystallization in massecuite is controlled at 60%, obtains the sodium wolframate crystallization, after filtering, the pure water that is 1.5:1 with liquid-solid ratio dissolves, and solution carries out ion-exchange removal of impurities for the second time more afterwards; Exchange for the second time removal of impurities, with 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 is controlled its pH value 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 APT separates out when pH is down to 7.0, as (NH
4)
2WO
4Solution density is 1.06g/m
3The time, stopped heating, cooling 0.5h, cooled solution is drained into vacuumfilter carry out filtration washing, the APT percent crystallization in massecuite is controlled at and obtains wet APT below 70%, and is dry at 90 ℃ of temperature, sieving is packaged to be the APT finished product after mixing, and the weight of the APT finished product that obtains is 3.808kg.
In the present embodiment, WO
3The rate of recovery reach 95.2%.
Embodiment 2:
A. abrasive material and batching: the useless low tungsten sizing of APT to-125 orders 〉=90%, is got 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 for 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 be 900-950 ℃, pressure be-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, generation sintered material after calcining is completed;
C. wet-milling and filtration: sintered material is added the softening water wet-milling, and liquid-solid ratio is 1.85:1, and the slip that grinds boils 2h with the 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, with 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 1-2 drip washing, NaOH solution with 40g/L carries out desorb again, the sodium tungstate solution of desorb gained, and the pH value is greater than 9, carry out evaporation concentration by traditional technology this moment, the sodium wolframate percent crystallization in massecuite is controlled at 70%, obtains the sodium wolframate crystallization, after filtering, the pure water that is 2.0:1 with liquid-solid ratio dissolves, and solution carries out ion-exchange removal of impurities for the second time more afterwards; Exchange for the second time removal of impurities, with 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 is controlled its pH value 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 APT separates out when pH is down to 7.7, as (NH
4)
2WO
4Solution density is 1.12g/m
3The time, stopped heating, cooling 0.5h, cooled solution is drained into vacuumfilter carry out filtration washing, the APT percent crystallization in massecuite is controlled at and obtains wet APT below 70%, and is dry at 120 ℃ of temperature, sieving is packaged to be the APT finished product after mixing, and the weight of the APT finished product that obtains is 7.736kg.
In the present embodiment, WO
3The rate of recovery reach 96.7%.
Embodiment 3:
A. abrasive material and batching: the useless low tungsten sizing of APT to-125 orders 〉=90%, is got 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 for 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 be 850-900 ℃, pressure be-150--180Pa; The temperature out of preheater be 245-270 ℃, inlet pressure be-140--190Pa, top hole pressure be-7100--7300Pa; The temperature of kiln head cover is 750-780 ℃; Calcination time is 1.8h, generation sintered material after calcining is completed;
C. wet-milling and filtration: sintered material is added the softening water wet-milling, and liquid-solid ratio is 1.76:1, and the slip that grinds boils 1.7h with the 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, with 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 1-2 drip washing, NaOH solution with 40g/L carries out desorb again, the sodium tungstate solution of desorb gained, and the pH value is greater than 9, carry out evaporation concentration by traditional technology this moment, the sodium wolframate percent crystallization in massecuite is controlled at 65%, obtains the sodium wolframate crystallization, after filtering, the pure water that is 1.7:1 with liquid-solid ratio dissolves, and solution carries out ion-exchange removal of impurities for the second time more afterwards; Exchange for the second time removal of impurities, with 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 is controlled its pH value 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 APT separates out when pH is down to 7.3, as (NH
4)
2WO
4Solution density is 1.08g/m
3The time, stopped heating, cooling 0.5h, cooled solution is drained into vacuumfilter carry out filtration washing, the APT percent crystallization in massecuite is controlled at and obtains wet APT below 70%, and is dry at 100 ℃ of temperature, sieving is packaged to be the APT finished product after mixing, and the weight of the APT finished product that obtains 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.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, improve 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. method of utilizing the useless low tungsten slag regeneration APT of APT, it is characterized in that: its step is as follows:
A. abrasive material and batching: with the useless low tungsten sizing of APT to-125 orders 〉=90%, WO in useless low tungsten slag charge
3Grade be formulated to 4-8%, prepare burden afterwards, the 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 for preparing in step a is calcined, generated sintered material;
C. wet-milling and filtration: sintered material is added the softening water wet-milling, and liquid-solid ratio is 1.70:1-1.85:1, and the slip that grinds boils 1.6-2h with the 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, with WO in step c coarse sodium tungstate
3Concentration dilution below 30g/L, after exchange resin is saturated, NaOH solution with concentration 25g/L is made eluent, exchange resin is carried out 1-2 drip washing, NaOH solution with 40g/L carries out desorb again, the sodium tungstate solution of desorb gained, the pH value is greater than 9, carry out evaporation concentration by traditional technology this moment, the sodium wolframate percent crystallization in massecuite is controlled at 60%-70%, obtains the sodium wolframate crystallization, after filtering, the pure water that is 1.5:1-2.0:1 with liquid-solid ratio dissolves, and solution carries out ion-exchange removal of impurities for the second time more afterwards; Exchange for the second time removal of impurities, with 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 is controlled its pH value 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 APT separates out when pH is down to 7.0-7.7, as (NH
4)
2WO
4Solution density is 1.06-1.12g/m
3The time, stopped heating, cooling 0.5h drains into vacuumfilter with cooled solution and carries out filtration washing, and the APT percent crystallization in massecuite is controlled at and obtains wet APT below 70%, and is dry at 90-120 ℃ of temperature, sieves to be packaged to be the APT finished product after mixing.
2. a kind of method of utilizing the useless low tungsten slag regeneration APT of APT according to claim 1, it is characterized in that: in step b, the slag charge for 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, the temperature of kiln tail smoke-box be 800-950 ℃, pressure be-110--190Pa; The temperature out of preheater be 230-280 ℃, inlet pressure be-120--200Pa, top hole pressure be-7000--7500Pa; The temperature of kiln head cover is 700-800 ℃, and calcination time is 1.6-2.5h, generation sintered material after calcining is completed.
3. a kind of method of utilizing the useless low tungsten slag regeneration APT of APT according to claim 1, it is characterized in that: in step c, sintered material is first added the softening water wet-milling through rod mill, the slip that grinds flows in steel basin and boils 1.5-2h with the 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 APT of APT according to claim 1, it is characterized in that: in steps d, what two secondary ions exchange removal of impurities were adopted is 201 * 7 type Strong basic anion exchange resins.
5. a kind of method of utilizing the useless low tungsten slag regeneration of APT APT according to claim 1, is characterized in that: in step a ,-125 orders 〉=90% is arrived in the useless low tungsten sizing of APT, WO in useless low tungsten slag charge
3Grade to be formulated to 6%, the soda add-on is WO
3140% of theoretical amount, nitre add-on are WO
32.1% of theoretical amount; In step b, the slag charge for preparing in step a is calcined in rotary kiln, its burning zone temperature is 1100-1250 ℃, the rotating speed of rotary kiln is 0.9r/min, the temperature of kiln tail smoke-box be 850-900 ℃, pressure be-150--180Pa; The temperature out of preheater be 245-270 ℃, inlet pressure be-140--190Pa, top hole pressure be-7100--7300Pa; The temperature of kiln head cover is 750-780 ℃; Calcination time is 1.8h; In step c, sintered material is added the softening water wet-milling, liquid-solid ratio is 1.76:1, and the slip that grinds boils 1.7h with the 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, the sodium wolframate percent crystallization in massecuite is controlled at 65%, obtains the sodium wolframate crystallization, and after filtering, the pure water that is 1.7:1 with liquid-solid ratio dissolves; NH with 25g/L
4Cl solution is made strippant, carries out desorb, obtains (NH
4)
2WO
4Solution; In step e, APT separates out when pH is down to 7.3, as (NH
4)
2WO
4Solution density is 1.08g/m
3The time, stopped heating, cooling 0.5h drains into vacuumfilter with material and carries out filtration washing, and the APT percent crystallization in massecuite is controlled at below 70%, and the wet APT that obtains is after drying at 100 ℃ of temperature, and sieving is packaged to be the APT finished product after mixing.
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