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 PDF

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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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apt
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陈泉兴
张中山
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陈泉兴
张中山
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    • YGENERAL 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
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    • Y02P10/20Recycling

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

A kind of method of utilizing the useless low tungsten slag regeneration of APT APT
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.
CN201210479921.1A 2012-11-23 2012-11-23 Method for regenerating APT (ammonium paratungstate) by use of APT waste low-grade tungsten slag Expired - Fee Related CN103103359B (en)

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103523800A (en) * 2013-09-24 2014-01-22 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
CN104046800A (en) * 2014-07-11 2014-09-17 谭春波 Process of extracting white tungsten concentrate from tungstenic iron ores or tungstenic waste residues
CN104263971A (en) * 2014-10-09 2015-01-07 中南大学 System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material with zero pollution
CN104263972A (en) * 2014-10-09 2015-01-07 中南大学 Metallurgy system with multiple closed cycles for tungsten mineral raw materials
CN104263973A (en) * 2014-10-09 2015-01-07 江西稀有金属钨业控股集团有限公司 Method for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops
CN104263975A (en) * 2014-10-09 2015-01-07 江西稀有金属钨业控股集团有限公司 Metallurgical technology with multiple closed cycles for tungsten mineral raw materials
CN104263974A (en) * 2014-10-09 2015-01-07 江西稀有金属钨业控股集团有限公司 Method for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material with zero waste water discharge
CN104263976A (en) * 2014-10-09 2015-01-07 江西稀有金属钨业控股集团有限公司 Tungsten mineral raw material metallurgical process capable of realizing no pollution discharge in whole process
CN104630490A (en) * 2015-02-10 2015-05-20 江西稀有金属钨业控股集团有限公司 Method for preparing ammonium tungstate
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
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
CN106379941A (en) * 2016-10-12 2017-02-08 佛山迅拓奥科技有限公司 Preparation method of high-purity tungsten trioxide
CN106435224A (en) * 2016-08-17 2017-02-22 湖南金源新材料股份有限公司 Method for preparing ammonium paratungstate from waste containing tungsten
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
CN110343857A (en) * 2019-07-15 2019-10-18 厦门钨业股份有限公司 The method for handling tungsten ore
CN110735052A (en) * 2019-10-16 2020-01-31 清远市恒德环保科技有限公司 Method for enriching tungsten in low-grade APT slag

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303622A (en) * 1981-01-19 1981-12-01 Amax Inc. Chemical treatment of low-grade wolframite concentrate having high Mo/WO3 ratio
CN1037882A (en) * 1988-04-29 1989-12-13 阿托化学公司 The method for preparing iron(ic) chloride by dilute 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
CN101333598A (en) * 2008-01-17 2008-12-31 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
CN101565778A (en) * 2009-05-22 2009-10-28 中南大学 Method for depositing and separating tungsten and molybdenum in tungstate/molybdate mixed solution
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
CN102071313A (en) * 2011-01-29 2011-05-25 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
CN102212697A (en) * 2011-05-18 2011-10-12 湖南稀土金属材料研究院 Tungsten slag treatment method
EP2450312A1 (en) * 2010-11-03 2012-05-09 Montanuniversität Leoben Recovery of tungsten from waste material by ammonium leaching

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303622A (en) * 1981-01-19 1981-12-01 Amax Inc. Chemical treatment of low-grade wolframite concentrate having high Mo/WO3 ratio
CN1037882A (en) * 1988-04-29 1989-12-13 阿托化学公司 The method for preparing iron(ic) chloride by dilute 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
CN101333598A (en) * 2008-01-17 2008-12-31 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
CN101565778A (en) * 2009-05-22 2009-10-28 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
CN102071313A (en) * 2011-01-29 2011-05-25 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
CN102212697A (en) * 2011-05-18 2011-10-12 湖南稀土金属材料研究院 Tungsten slag treatment method

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103523800A (en) * 2013-09-24 2014-01-22 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
CN104046800A (en) * 2014-07-11 2014-09-17 谭春波 Process of extracting white tungsten concentrate from tungstenic iron ores or tungstenic waste residues
CN104263974A (en) * 2014-10-09 2015-01-07 江西稀有金属钨业控股集团有限公司 Method for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material with zero waste water discharge
CN104263972A (en) * 2014-10-09 2015-01-07 中南大学 Metallurgy system with multiple closed cycles for tungsten mineral raw materials
CN104263973A (en) * 2014-10-09 2015-01-07 江西稀有金属钨业控股集团有限公司 Method for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material by multiple closed loops
CN104263975A (en) * 2014-10-09 2015-01-07 江西稀有金属钨业控股集团有限公司 Metallurgical technology with multiple closed cycles for tungsten mineral raw materials
CN104263971A (en) * 2014-10-09 2015-01-07 中南大学 System for preparing APT (Ammonium Paratungstate) from tungsten mineral raw material with zero pollution
CN104263976A (en) * 2014-10-09 2015-01-07 江西稀有金属钨业控股集团有限公司 Tungsten mineral raw material metallurgical process capable of realizing no pollution discharge in whole process
CN104263971B (en) * 2014-10-09 2016-08-24 中南大学 The system of APT is prepared by tungsten mineral material no pollution
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
CN104630490A (en) * 2015-02-10 2015-05-20 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
CN106435224A (en) * 2016-08-17 2017-02-22 湖南金源新材料股份有限公司 Method for preparing ammonium paratungstate from waste containing tungsten
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
CN106379941A (en) * 2016-10-12 2017-02-08 佛山迅拓奥科技有限公司 Preparation method of high-purity tungsten trioxide
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
CN110343857A (en) * 2019-07-15 2019-10-18 厦门钨业股份有限公司 The method for handling tungsten ore
CN110735052A (en) * 2019-10-16 2020-01-31 清远市恒德环保科技有限公司 Method for enriching tungsten in low-grade APT slag
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

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