CN101723463B - Method and device for preparing tungstic acid through closed type acid decomposition of wolframite - Google Patents
Method and device for preparing tungstic acid through closed type acid decomposition of wolframite Download PDFInfo
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- CN101723463B CN101723463B CN2008100719368A CN200810071936A CN101723463B CN 101723463 B CN101723463 B CN 101723463B CN 2008100719368 A CN2008100719368 A CN 2008100719368A CN 200810071936 A CN200810071936 A CN 200810071936A CN 101723463 B CN101723463 B CN 101723463B
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Abstract
The invention relates to a method and a device for preparing tungstic acid through closed type acid decomposition of wolframite. The method adopts closed type acidification reaction, and ammonium nitrate is added in the process step of the acidification reaction. The method comprises the following steps of: performing stirring dissolution and heating; performing the acidification reaction, namelyperforming the acidification reaction under a condition with the temperature of between 100 and 130 DEG C and the pressure of between 0.1 to 0.3 MPa; performing washing and dehydration; and performing drying and packaging to obtain a finished product of the tungstic acid. The device for implementing the method for preparing the tungstic acid through the closed type acid decomposition of the wolframite comprises a pump, a cooler, a sewage treatment tank, a potcher, a reaction vessel body and a stirrer, wherein the inlet of the reaction vessel body is provided with a cover flange and a cover, and an outlet of the reaction vessel body is provided with an outlet flange; an inner liner of the reaction vessel body is provided with a graphite brick middle layer and a rubber lining; the cover is provided with a valve communicated with the pump and a valve communicated with the cooler; a bracket is symmetrically arranged outside the reaction vessel body; and the stirrer is sleeved with a rubber bush. The method and the device have the advantages of stable product quality, low energy consumption, safety, environmental protection, obvious economic benefit and the like.
Description
One. technical field
The present invention relates to metallurgical technology field, especially a kind of method and apparatus of preparing tungstic acid through closed type acid decomposition of wolframite.
Two. background technology
Wolframic acid is a kind of oxide compound of tungsten, and normal temperature is yellow powder shape, molecular formula: H down
2WO
4, be mainly used in the catalyst field of fine chemistry industry.
The method for preparing tungstenic acid product has two kinds: the one, and be the classical technology of raw material with the wolframite; The 2nd, be the acid system production technique of raw material with the sheelite.The classical technology that mainly with the wolframite is raw material at present is main, concrete technical process is: ball milling → soda boiling → purification → white tungsten → acidifying → dewatered drying → packing, wherein acidizing process adopts the open type acidification reaction, promptly under normal pressure, carry out, earlier hydrochloric acid is added in the enamel reactor and heat, then calcium wolframate and nitric acid adding are carried out reacting by heating, hydrochloric acid and nitric acid add with liquid state, because hydrochloric acid and nitric acid are volatile product, it is high to cause hydrochloric acid and nitric acid to consume, owing to be that unlimited heating energy consumption is also high, hydrochloric acid and nitric acid volatilization can cause environmental pollution simultaneously, and enterprise's production cost is high.With the equipment of this classics process matching be the enamel reactor, with the agitator of enamel lining, because adopting to open wide, hydrochloric acid and nitric acid adds, corrodibility is big, the enamel of reactor inwall and agitator is perishable to come off, work-ing life is short, and hydrochloric acid and nitric acid are corrosive liquid simultaneously, and is dangerous big, open wide adding because hydrochloric acid and nitric acid adopt simultaneously, the operator is easily spattered wound.Some enterprises are by changing the reactor inwall into the tetrafluoro lining by original enamel, but the tetrafluoro that is served as a contrast easily comes off, and equipment is short duration of service; Also have some enterprises by the change technical recipe, but the tungstenic acid product quality instability of producing.The patent that Chinese patent discloses a kind of " method of producing tungstic acid by closed type hydrochloric acid decompose tunstite ", publication number is: 1414120, application is artificial: Sichuan Zigong Hard Alloy Co., Ltd, this method is to be that raw material is produced tungstenic acid product with the sheelite, the tungstenic acid product quality instability of being produced, the said firm has stopped producing wolframic acid at present.
Therefore seeking a kind of constant product quality, energy consumption wolframic acid preparation method and equipment low, safety and environmental protection of making just seems particularly urgent and important.
Three. summary of the invention
The object of the present invention is to provide a kind of method and apparatus of preparing tungstic acid through closed type acid decomposition of wolframite, can make constant product quality, low, the safety and environmental protection of energy consumption.
For reaching this purpose, the present invention mainly finishes in the following way:
The method of preparing tungstic acid through closed type acid decomposition of wolframite is to adopt the closed acidification reaction, adds ammonium nitrate in the acidification reaction operation, and this method comprises following processing steps in sequence and condition:
A. stirring and dissolving and heating carried out stirring and dissolving with ammonium nitrate, calcium wolframate slip, in addition hydrochloric acid pumped into reactor and heats;
B. acidification reaction, with the ammonium nitrate after the stirring and dissolving, the hydrochloric acid stirring heating of calcium wolframate slip after heating, the ammonium nitrate add-on is pressed WO in the calcium wolframate slip
37～10% of content adds, and carries out acidification reaction under 100～130 ℃, 0.1～0.3MPa condition, and reaction 15～30min stops heating;
C. washing dehydration is put into rinse tank with the material of acidification reaction from the reactor bottom, carries out washing dehydration with deionized water;
D. drying and packaging carries out drying and packaging with the wolframic acid behind the washing dehydration, promptly gets the wolframic acid finished product.Be used to realize that the equipment of preparing tungstic acid through closed type acid decomposition of wolframite method comprises: pump, water cooler, treatment tank, rinse tank, reactor pot body, agitator, be provided with pot cover flange and pot cover at reactor pot body inlet, can pump into ammonium nitrate, calcium wolframate slip after the stirring and dissolving from the pot cover flange; The outlet of reactor pot body is provided with discharge flange, can be from outlet at bottom flange blowing; Be lined with graphite brick middle level and rubber lining in the reactor pot body, vapour passage can transmit heat preferably and prevent corrosion between reactor pot body and graphite brick middle level; Pot cover is provided with the valve that a valve and that is communicated with pump is communicated with water cooler, hydrochloric acid can be pumped into reactor and make tail gas enter water cooler; The external support that is arranged with of reactor pot; Agitator is with rubber bushing.Advantage of the present invention: 1. all processes are to carry out in confined conditions, have improved the phenomenon of evaporating, emitting, dripping or leaking of liquid or gas.
2. reactor has prolonged work-ing life by changing the inner foundation material.
3. reduce hydrochloric acid and coal consumption amount more than 10%.
4. replace nitric acid with ammonium nitrate, ammonium nitrate is a solid, and is not volatile, and tail gas adopts the salt acid cooler to reclaim, and has reduced environmental pollution.
5. simple, the processing ease of constant product quality, technology, good reliability.
6. economic benefit is obvious, and the wolframic acid cost can reduce by 800～1000 yuan/ton.
Four. description of drawings
Fig. 1 is the process flow sheet according to a kind of preparing tungstic acid through closed type acid decomposition of wolframite provided by the invention.
Fig. 2 is a kind of preparing tungstic acid through closed type acid decomposition of wolframite equipment synoptic diagram that is used to realize the inventive method.
Sign symbol among the figure is represented respectively:
1. ammonium nitrate 2. calcium wolframate slips 3. hydrochloric acid 4. wolframic acid finished products 5. deionized waters 6. reactor pot bodies 7. graphite brick middle levels 8. rubber linings, 9. supports, 10. pot cover flanges, 11. pot covers, 12. discharge flanges
Five. embodiment
As shown in Figure 1, the method for preparing tungstic acid through closed type acid decomposition of wolframite is to adopt the closed acidification reaction, adds ammonium nitrate in the acidification reaction operation, and this method comprises following processing steps in sequence and condition:
A. stirring and dissolving and heating carried out stirring and dissolving with ammonium nitrate 1, calcium wolframate slip 2, in addition hydrochloric acid 3 pumped into reactor and heats;
B. acidification reaction, with the ammonium nitrate after the stirring and dissolving 1, hydrochloric acid 3 stirring heating of calcium wolframate slip 2 after heating, ammonium nitrate 1 add-on is pressed WO in the calcium wolframate slip 2
37～10% of content adds, and carries out acidification reaction under 100～130 ℃, 0.1～0.3MPa condition, and reaction 15～30min stops heating;
C. washing dehydration is put into rinse tank with the material of acidification reaction from the reactor bottom, carries out washing dehydration with deionized water;
D. drying and packaging carries out drying and packaging with the wolframic acid behind the washing dehydration, promptly gets wolframic acid finished product 4.
This method further comprises following processing steps in sequence and condition:
A. stirring and dissolving and heating is heated to 50～60 ℃ with hydrochloric acid 3;
B. acidification reaction, the concentration that adds hydrochloric acid 3 is 31%, add-on is 44～48% of calcium wolframate slip 2 amounts;
C. washing dehydration is heated to 80～100 ℃ with deionized water.
Be used to realize claim 1 or 2 described preparing tungstic acid through closed type acid decomposition of wolframite equipment, this equipment comprises: pump, water cooler, treatment tank, rinse tank, reactor pot body 6, agitator, reactor pot body 6 inlets are provided with pot cover flange 10 and pot cover 11, can pump into ammonium nitrate 1, calcium wolframate slip 2 after the stirring and dissolving from pot cover flange 10, outlet is provided with discharge flange 12, can be from discharge flange 12 blowings; Be lined with graphite brick middle level 7 and rubber lining 8 in the reactor pot body 6, vapour passage can transmit heat preferably and prevent corrosion between reactor pot body 6 and graphite brick middle level 7; Pot cover 11 is provided with the valve that a valve and that is communicated with pump is communicated with water cooler, hydrochloric acid 3 can be pumped into reactor and make tail gas enter water cooler; 6 external symmetrys of reactor pot body are provided with support 9; Agitator is with rubber bushing.
This equipment further comprises: rubber lining 8 and graphite brick middle level 7, rubber bushing respectively are 1～2 layer.
Fill hydrochloric acid in the described water cooler, hydrochloric acid mixes the waste liquid that produces as the neutralizing agent treatment tank that refluxes with waste gas.
Resin impregnating is used in described graphite brick middle level 7.
Example one
Use method and apparatus of the present invention, ammonium nitrate 1 is added 700 liters of calcium wolframate slips 2 that the reaction washing is good, the WO3 content in the calcium wolframate slip 2 is 180 kilograms, and the 7-10% that ammonium nitrate 1 add-on is pressed WO3 content adds; 330 liter 31% normal temperature hydrochloric acid 3 is pumped in the reactor, start device for recovering tail gas, open steam heating and stop heating after 5～10 minutes, ammonium nitrate after the stirring and dissolving 1, calcium wolframate slip 2 are pumped in the reactor, turn off imported valve, open steam and continued reacting by heating 15～30 minutes, reaction Shu Houcong outlet at bottom flange 12 blowings are to rinse tank, carry out washing dehydration with 80～100 ℃ of deionized waters 5, carry out drying and packaging again, wolframic acid finished product 4 quantity are 200 kilograms through weighing.
Example two
Use method and apparatus of the present invention, ammonium nitrate 1 is added 700 liters of calcium wolframate slips 2 that the reaction washing is good, WO3 content is 180 kilograms in the calcium wolframate slip 2, pumps into reactor, and ammonium nitrate 1 is pressed 8～9% of WO3 content and added; 310 liter 31% normal temperature hydrochloric acid 3 is pumped into reactor, start device for recovering tail gas, open steam heating and stop heating after 5～10 minutes, ammonium nitrate after the stirring and dissolving 1, calcium wolframate slip 2 are pumped into reactor, turn off the valve that pot cover 11 is communicated with pump, open steam and continued reacting by heating 15～30 minutes, reaction finishes the back and washs dehydration then from the bottom blowing to rinse tank with 80～100 ℃ of deionized waters 5, carry out drying and packaging again, wolframic acid finished product 4 quantity are 200 kilograms through weighing.
The product that above-mentioned two examples are produced is through sampling inspection and relatively physics and the not change of chemical property of the classical technology of background, and quality product is all qualified.The entire operation process is carried out in confined conditions, replace nitric acid with ammonium nitrate, hydrochloric acid and calcium wolframate directly pump in the reactor by pump, all feed liquids adopt airtight adding, and the operator is difficult for injured, have improved Working environment greatly, tail gas is recycled again, the consumption of hydrochloric acid and coal reduces, and has reduced production cost, and each economic target reaches its intended purposes.
Claims (6)
1. the method for preparing tungstic acid through closed type acid decomposition of wolframite is to adopt the closed acidification reaction, adds ammonium nitrate in the acidification reaction operation, and this method comprises following processing steps in sequence and condition:
A. stirring and dissolving and heating carried out stirring and dissolving with ammonium nitrate (1), calcium wolframate slip (2), in addition hydrochloric acid (3) pumped into reactor and heats;
B. acidification reaction, with the ammonium nitrate after the stirring and dissolving (1), hydrochloric acid (3) stirring heating of calcium wolframate slip (2) after heating, ammonium nitrate (1) add-on press the middle WO of calcium wolframate slip (2)
37～10% of content adds, and carries out acidification reaction under 100～130 ℃, 0.1～0.3MPa condition, and reaction 15～30min stops heating;
C. washing dehydration is put into rinse tank with the material of acidification reaction from the reactor bottom, carries out washing dehydration with deionized water;
D. drying and packaging carries out drying and packaging with the wolframic acid behind the washing dehydration, promptly gets wolframic acid finished product (4).
2. the method for preparing tungstic acid through closed type acid decomposition of wolframite according to claim 1 is characterized in that this method further comprises following processing steps in sequence and condition:
A. stirring and dissolving and heating is heated to 50～60 ℃ with hydrochloric acid (3);
B. acidification reaction, the concentration that adds hydrochloric acid (3) is 31%, add-on is 44～48% of calcium wolframate slip (a 2) amount;
C. washing dehydration is heated to 80～100 ℃ with deionized water.
3. be used to realize the equipment of the method for claim 1 or 2 described preparing tungstic acid through closed type acid decomposition of wolframite, this equipment comprises: pump, water cooler, treatment tank, rinse tank, reactor pot body (6), agitator, it is characterized in that reactor pot body (6) inlet is provided with pot cover flange (10) and pot cover (11), can pump into ammonium nitrate (1), calcium wolframate slip (2) after the stirring and dissolving from pot cover flange (10); Reactor pot body (6) outlet is provided with discharge flange (12), can be from discharge flange (12) blowing; Be lined with graphite brick middle level (7) and rubber lining (8) in the reactor pot body (6), vapour passage can transmit heat preferably and prevent corrosion between reactor pot body (6) and graphite brick middle level (7); Pot cover (11) is provided with the valve that a valve and that is communicated with pump is communicated with water cooler, hydrochloric acid (3) can be pumped into reactor and make tail gas enter water cooler; Reactor pot body (6) external symmetry is provided with support (9); Agitator is with rubber bushing.
4. equipment according to claim 3, this equipment further comprises: rubber lining (8) and graphite brick middle level (7), rubber bushing respectively are 1～2 layer.
5. equipment according to claim 3 fills hydrochloric acid in the described water cooler, and hydrochloric acid mixes the waste liquid that produces as the neutralizing agent treatment tank that refluxes with tail gas.
6. equipment according to claim 4, resin impregnating is used in described graphite brick middle level (7).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100719368A CN101723463B (en) | 2008-10-14 | 2008-10-14 | Method and device for preparing tungstic acid through closed type acid decomposition of wolframite |
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| CN2008100719368A CN101723463B (en) | 2008-10-14 | 2008-10-14 | Method and device for preparing tungstic acid through closed type acid decomposition of wolframite |
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|---|---|
| CN101723463A CN101723463A (en) | 2010-06-09 |
| CN101723463B true CN101723463B (en) | 2011-06-15 |
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| CN2008100719368A Expired - Fee Related CN101723463B (en) | 2008-10-14 | 2008-10-14 | Method and device for preparing tungstic acid through closed type acid decomposition of wolframite |
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| CN106512721A (en) * | 2016-12-14 | 2017-03-22 | 衡阳市南东有色金属有限公司 | Improved waste gas treatment system for ammonium paratungstate production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4629503A (en) * | 1985-04-17 | 1986-12-16 | Ramot - University Authority For Applied Research And Industrial Development | Process for the recovery of tungsten in a pure form from tungsten-containing materials |
| US4975167A (en) * | 1985-10-15 | 1990-12-04 | Mta Kozponti Fizikai Kutato Intezete | Process for production of pure tungstic acid or molybdic acid from impure alkali metal tungstate or molybdate solutions |
| CN1414120A (en) * | 2002-11-15 | 2003-04-30 | 自贡硬质合金有限责任公司 | Method of producing tungstic acid by closed type hydrochloric acid decompose tunstite |
| CN101224906A (en) * | 2008-02-01 | 2008-07-23 | 福建金鑫钨业有限公司 | Method for preparing low apparent density wolframic acid |
-
2008
- 2008-10-14 CN CN2008100719368A patent/CN101723463B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4629503A (en) * | 1985-04-17 | 1986-12-16 | Ramot - University Authority For Applied Research And Industrial Development | Process for the recovery of tungsten in a pure form from tungsten-containing materials |
| US4975167A (en) * | 1985-10-15 | 1990-12-04 | Mta Kozponti Fizikai Kutato Intezete | Process for production of pure tungstic acid or molybdic acid from impure alkali metal tungstate or molybdate solutions |
| CN1414120A (en) * | 2002-11-15 | 2003-04-30 | 自贡硬质合金有限责任公司 | Method of producing tungstic acid by closed type hydrochloric acid decompose tunstite |
| CN101224906A (en) * | 2008-02-01 | 2008-07-23 | 福建金鑫钨业有限公司 | Method for preparing low apparent density wolframic acid |
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Denomination of invention: Method and device for preparing tungstic acid through closed type acid decomposition of wolframite Effective date of registration: 20150623 Granted publication date: 20110615 Pledgee: Agricultural Bank of China, Limited by Share Ltd, Longyan branch Pledgor: Fujian Jinxin Tungsten Co., Ltd Registration number: 2015990000497 |
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