CN104030254A - Fluorine-chlorine removal and recovery device in copper smelting smoke acid making system and recovery method thereof - Google Patents
Fluorine-chlorine removal and recovery device in copper smelting smoke acid making system and recovery method thereof Download PDFInfo
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- CN104030254A CN104030254A CN201410260042.9A CN201410260042A CN104030254A CN 104030254 A CN104030254 A CN 104030254A CN 201410260042 A CN201410260042 A CN 201410260042A CN 104030254 A CN104030254 A CN 104030254A
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- fluorine
- fluorine chlorine
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention provides a fluorine-chlorine removal and recovery device in a copper smelting smoke acid making system and a recovery method thereof. The air is heated to 120-180 DEG C by an external heat exchanger by using the waste heat of a sulfuric acid conversion system, and the air is supplied to a fluorine-chlorine removal tower by an air blower; hot air and copper smelting waste acid are in reverse contact in the fluorine-chlorine removal tower, and copper smelting waste acid is quickly heated to 60-100 DEG C; fluorine and chlorine in purifying waste acid of the copper smelting smoke acid making system are separated out in a gas form of hydrogen fluoride and hydrogen chloride; separated hydrogen fluoride and hydrogen chloride enter a fluorine-chlorine absorption tower along with the hot air and are absorbed in the fluorine-chlorine absorption tower. In the invention, fluorine and chlorine can be removed without adding any drug such as a fluorine removal agent, a chlorine removal agent and the like in the recovery process, so that the production cost can be reduced. The removed fluorine and chlorine can be recycled and made into calcium fluoride, and the product has relatively high added values and remarkable economic benefits; in traditional fluorine removal, fluorine is discarded, thereby causing resource waste and environmental pollution.
Description
Technical field
The present invention relates to fluorine chlorine in spent acid and remove recovery technology field, be specifically related to a kind ofly complete fluorine chlorine in the copper metallurgical gas sulphuric acid system that fluorine chlorine reclaims by sorption after not adding fluorine chlorinolysis that any medicament completes the spent acid in copper metallurgical gas sulphuric acid system and analysing and remove retrieving arrangement and recovery method thereof.
Background technology
Fluorine in copper flue gas during smelting and chlorine are in diluted acid purification and washing process, and fluorine and chlorine are present in and purify in spent acid with the form of hydrofluoric acid and hydrochloric acid.The corrodibility of hydrofluoric acid is very strong, and in flue gas, hydrogen fluoride exceeds standard and can cause the corrosion of ceramic packing in drying tower, absorption system.Hydrochloric acid is stronger to the corrodibility of sulfate system steel pipeline.In current technique, hydrofluoric removal is to add bath of glass or in dynamic wave scrubber, stack ceramic packing to complete solid fluorine.Because bath of glass viscosity is larger, in course of conveying, easily cause line clogging, and winter, liquid easily froze, and may cause bath of glass to add.Hydrochloric acid is removed without better method, by spent acid operation neutralizing treatment.This removal method has caused the significant wastage of resource, has increased production cost.
At present, the patent of invention " defluorination method in a kind of pyrite-based sulfuric acid production " that publication number is CN101591007, adopts and adds water glass as precipitation agent, fluorine to be precipitated in pyrite-based sulfuric acid production system spent acid.The method in actual production process, content the unknown of fluorine in spent acid, water glass add-on is completely rule of thumb controlled, and may cause removal efficiency of flouride lower, causes the corrosion of responsibility system and device.
Summary of the invention
Technical problem to be solved by this invention be provide for shortcoming of the prior art a kind of by physical method do not add any additive complete washing spent acid in fluorine chlorine desorption copper metallurgical gas sulphuric acid system purify in spent acid fluorine chlorine remove retrieving arrangement, the present invention also provides the recovery method of above-mentioned retrieving arrangement.
Adopt following technical scheme for solving technical problem of the present invention:
In a kind of copper metallurgical gas sulphuric acid system, fluorine chlorine removes retrieving arrangement, comprise gas blower, fluorine chlorine removes tower, spent acid acid trap, fluorine chlorine absorption tower, solid-liquid separating equipment, described blower export removes tower gas phase entrance with fluorine chlorine and is connected, described fluorine chlorine removes middle portion in tower and loads fire resistant polypropylene Haier ring, described fire resistant polypropylene Haier's ring top arranges spent acid acid trap, described spent acid acid trap is positioned at fluorine chlorine and removes tower inner and upper, described fluorine chlorine removes tower gaseous phase outlet and is connected with fluorine chlorine absorption tower, the absorption agent on described fluorine chlorine absorption tower is calcium oxide and calcium chloride solution, described fluorine chlorine absorption tower is connected with solid-liquid separating equipment.
Described fluorine chlorine absorption tower is foam absorbing tower, and on fluorine chlorine absorption tower, air vout arranges wire mesh mist eliminator.
In copper metallurgical gas sulphuric acid system, fluorine chlorine removes the recovery method of retrieving arrangement, and its step is as follows:
Spent acid in step a, copper metallurgical gas sulphuric acid system enters fluorine chlorine by spent acid acid trap and removes in tower, and spent acid acid trap is evenly smelted copper spent acid and is distributed in fire resistant polypropylene Haier ring;
Step b, utilize gas blower to remove toward fluorine chlorine the warm air that tower passes into 120 DEG C-180 DEG C, copper in warm air and fire resistant polypropylene Haier ring smelts that spent acid is reverse to be contacted, make the copper smelting spent acid in fire resistant polypropylene Haier ring be heated to rapidly 60 DEG C-100 DEG C, fluorine and chlorine that copper metallurgical gas sulphuric acid system purifies in spent acid are separated out with the form of gas with hydrogen fluoride and hydrogenchloride, spent acid after de-fluorine and chlorine removal returns to spent acid operation, carries out neutralizing treatment;
Step c, hydrogen fluoride and hydrogenchloride are accompanied by warm air and remove tower gaseous phase outlet from fluorine chlorine and enter fluorine chlorine absorption tower, and the absorption agent calcium oxide on fluorine chlorine absorption tower and calcium chloride solution absorb hydrogen fluoride and hydrogenchloride, and reaction generates the solidliquid mixture of throw out Calcium Fluoride (Fluorspan);
The solid matter of the solidliquid mixture on steps d, fluorine chlorine absorption tower after solid-liquid separating equipment filtering separation is Calcium Fluoride (Fluorspan) product, and the liquid after filtering separation enters sewage disposal operation.
The present invention utilize sulfuric acid conversion system used heat through external heat exchanger to atmosphere temperature rising, make air themperature rise to 120 DEG C-180 DEG C, be sent to fluorine chlorine through gas blower and remove tower, warm air is smelted spent acid reverse contact in fluorine chlorine removes tower with copper, copper is smelted spent acid and is heated to rapidly 60 DEG C-100 DEG C, the fluorine chlorine that copper metallurgical gas sulphuric acid system purifies in spent acid is separated out with the form of gas with hydrogen fluoride and hydrogenchloride, the hydrogen fluoride of separating out and hydrogenchloride follow warm air to enter fluorine chlorine absorption tower, in fluorine chlorine absorption tower, there is following reaction in hydrogen fluoride and calcium chloride:
2HF+?CaCl
2=CaF
2↓+2HCl
2HF+?Ca(OH)
?2=CaF
2↓+2H
2O
By add calcium oxide in hydrogen fluoride absorption tower, there is reaction as follows:
CaO+H
2O=Ca(OH)
?2
Ca(OH)
?2+2HCl=CaCl
2+2H
2O
The Calcium Fluoride (Fluorspan) that reaction generates is throw out, and after solid-liquid separating equipment filtering separation, solid matter is Calcium Fluoride (Fluorspan) product, and the finally copper of de-fluorine and chlorine removal smelting spent acid returns to spent acid operation.
In copper metallurgical gas sulphuric acid system provided by the invention, fluorine chlorine removes retrieving arrangement and recovery method thereof, its advantage is: 1, traditional fluorine removes and need to add medicament, to reach the object of solid fluorine and defluorination, and the present invention does not need to add any medicament such as defluorinating agent and antichlor and just can reach the object of de-fluorine and chlorine removal in removal process, can reduce production costs.2, the fluorine chlorine recoverable that the present invention removes is made Calcium Fluoride (Fluorspan), and added value of product is larger, remarkable in economical benefits, and traditional defluorination is discarded by fluorine, causes the wasting of resources, by causing environmental pollution.
Brief description of the drawings
Fig. 1 is structural representation of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail:
As shown in Figure 1, a kind of copper metallurgical gas sulphuric acid system purifies fluorine chlorine in spent acid and removes retrieving arrangement, comprise gas blower 1, fluorine chlorine removes tower 2, spent acid acid trap 3, fluorine chlorine absorption tower 4, solid-liquid separating equipment 5, gas blower 1 exports and removes tower 2 gas phase entrances with fluorine chlorine and be connected, fluorine chlorine removes the interior middle portion of tower 2 and loads fire resistant polypropylene Haier ring 6, described fire resistant polypropylene Haier encircles 6 tops spent acid acid trap 3 is set, spent acid acid trap 3 is positioned at fluorine chlorine and removes tower 2 inner and upper, described fluorine chlorine removes tower 2 gaseous phase outlets and is connected with fluorine chlorine absorption tower 4, fluorine chlorine absorption tower 4 is foam absorbing tower, the absorption agent on fluorine chlorine absorption tower 4 is calcium oxide and calcium chloride, on fluorine chlorine absorption tower, 4 air vouts are installed wire mesh mist eliminator 7, go out the drop of carrying secretly in air.Fluorine chlorine absorption tower 4 is connected with solid-liquid separating equipment 5, because the Calcium Fluoride (Fluorspan) generating in fluorine chlorine absorption tower 4 is micro-soluble material in solution, carries out good separating effect by solid-liquid separating equipment 5.
embodiment 1
In copper metallurgical gas sulphuric acid system purification spent acid, fluorine chlorine removes a recovery method for retrieving arrangement, and its step is as follows:
Step a, copper smelting spent acid enter fluorine chlorine by spent acid acid trap 3 and remove in tower 2, and spent acid acid trap 3 is evenly smelted copper spent acid and is distributed in fire resistant polypropylene Haier ring 6;
Step b, utilize gas blower 1 to remove toward fluorine chlorine the warm air that tower 2 passes into 120 DEG C, copper in warm air and fire resistant polypropylene Haier ring 6 smelts that spent acid is reverse to be contacted, make the copper smelting spent acid in fire resistant polypropylene Haier ring 6 be heated to rapidly 60 DEG C-100 DEG C, fluorine and chlorine that copper is smelted in spent acid are separated out with the form of gas with hydrogen fluoride and hydrogenchloride, spent acid after de-fluorine and chlorine removal returns to spent acid operation, carries out neutralizing treatment;
Step c, hydrogen fluoride and hydrogenchloride are accompanied by warm air and remove tower 2 gaseous phase outlets from fluorine chlorine and enter fluorine chlorine absorption tower 4, the absorption agent calcium oxide on fluorine chlorine absorption tower 4 and calcium chloride solution absorb hydrogen fluoride and hydrogenchloride, and reaction generates the solidliquid mixture of throw out Calcium Fluoride (Fluorspan);
The solidliquid mixture on steps d, fluorine chlorine absorption tower 4 solid matter after solid-liquid separating equipment 5 filtering separation is Calcium Fluoride (Fluorspan) product; Liquid enters sewage disposal operation.
embodiment 2
In copper metallurgical gas sulphuric acid system purification spent acid, fluorine chlorine removes a recovery method for retrieving arrangement, and its step is as follows:
Step a, copper smelting spent acid enter fluorine chlorine by spent acid acid trap 3 and remove in tower 2, and spent acid acid trap 3 is evenly smelted copper spent acid and is distributed in fire resistant polypropylene Haier ring 6;
Step b, utilize gas blower 1 to remove toward fluorine chlorine the warm air that tower 2 passes into 180 DEG C, copper in warm air and fire resistant polypropylene Haier ring 6 smelts that spent acid is reverse to be contacted, make the copper smelting spent acid in fire resistant polypropylene Haier ring 6 be heated to rapidly 60 DEG C-100 DEG C, fluorine and chlorine that copper metallurgical gas sulphuric acid system purifies in spent acid are separated out with the form of gas with hydrogen fluoride and hydrogenchloride, spent acid after de-fluorine and chlorine removal returns to spent acid operation, carries out neutralizing treatment;
Step c, hydrogen fluoride and hydrogenchloride are accompanied by warm air and remove tower 2 gaseous phase outlets from fluorine chlorine and enter fluorine chlorine absorption tower 4, the absorption agent calcium oxide on fluorine chlorine absorption tower 4 and calcium chloride solution absorb hydrogen fluoride and hydrogenchloride, and reaction generates the solidliquid mixture of throw out Calcium Fluoride (Fluorspan);
The solidliquid mixture on steps d, fluorine chlorine absorption tower 4 solid matter after solid-liquid separating equipment 5 filtering separation is Calcium Fluoride (Fluorspan) product; Liquid enters sewage disposal operation.
Claims (3)
1. in a copper metallurgical gas sulphuric acid system, fluorine chlorine removes retrieving arrangement, it is characterized in that: comprise gas blower (1), fluorine chlorine removes tower (2), spent acid acid trap (3), fluorine chlorine absorption tower (4), solid-liquid separating equipment (5), described gas blower (1) outlet removes tower (2) gas phase entrance with fluorine chlorine and is connected, described fluorine chlorine removes the interior middle portion of tower (2) and loads fire resistant polypropylene Haier ring (6), described fire resistant polypropylene Haier's ring (6) top arranges spent acid acid trap (3), described spent acid acid trap (3) is positioned at fluorine chlorine and removes tower (2) inner and upper, described fluorine chlorine removes tower (2) gaseous phase outlet and is connected with fluorine chlorine absorption tower (4), the absorption agent on described fluorine chlorine absorption tower (4) is calcium oxide and calcium chloride solution, described fluorine chlorine absorption tower (4) is connected with solid-liquid separating equipment (5).
2. in copper metallurgical gas sulphuric acid system according to claim 1, fluorine chlorine removes retrieving arrangement, it is characterized in that: described fluorine chlorine absorption tower (4) is foam absorbing tower, and on fluorine chlorine absorption tower (4), air vout arranges wire mesh mist eliminator (7).
3. in copper metallurgical gas sulphuric acid system according to claim 1 and 2, fluorine chlorine removes the recovery method of retrieving arrangement, it is characterized in that step is as follows:
Step a, copper smelting spent acid enter fluorine chlorine by spent acid acid trap (3) and remove in tower (2), and spent acid acid trap (3) is evenly smelted copper spent acid and is distributed in fire resistant polypropylene Haier ring (6);
Step b, utilize gas blower (1) to remove the warm air that tower (2) passes into 120 DEG C-180 DEG C toward fluorine chlorine, copper in warm air and fire resistant polypropylene Haier ring (6) smelts that spent acid is reverse to be contacted, make the copper smelting spent acid in fire resistant polypropylene Haier ring (6) be heated to rapidly 60 DEG C-100 DEG C, fluorine and chlorine that copper metallurgical gas sulphuric acid system purifies in spent acid are separated out with the form of gas with hydrogen fluoride and hydrogenchloride, spent acid after de-fluorine and chlorine removal returns to spent acid operation, carries out neutralizing treatment;
Step c, hydrogen fluoride and hydrogenchloride are accompanied by warm air and remove tower (2) gaseous phase outlet from fluorine chlorine and enter fluorine chlorine absorption tower (4), the absorption agent calcium oxide on fluorine chlorine absorption tower (4) and calcium chloride solution absorb hydrogen fluoride and hydrogenchloride, and reaction generates the solidliquid mixture of throw out Calcium Fluoride (Fluorspan);
The solid matter of the solidliquid mixture on steps d, fluorine chlorine absorption tower (4) after solid-liquid separating equipment (5) filtering separation is Calcium Fluoride (Fluorspan) product, and the liquid after filtering separation enters sewage disposal operation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410260042.9A CN104030254B (en) | 2014-06-12 | 2014-06-12 | In copper blast furnace off-gas acid making system, fluorine chlorine removes retrieving arrangement and recovery method thereof |
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|---|---|---|---|
| CN201410260042.9A CN104030254B (en) | 2014-06-12 | 2014-06-12 | In copper blast furnace off-gas acid making system, fluorine chlorine removes retrieving arrangement and recovery method thereof |
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| CN104030254A true CN104030254A (en) | 2014-09-10 |
| CN104030254B CN104030254B (en) | 2016-02-24 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105797540A (en) * | 2014-12-27 | 2016-07-27 | 江苏振方生物化学有限公司 | Method for absorbing exhaust from chlorobenzotrifluoride synthesis |
| CN106823759A (en) * | 2017-02-28 | 2017-06-13 | 中国恩菲工程技术有限公司 | Defluorinate chlorine device |
| CN114906823A (en) * | 2022-05-07 | 2022-08-16 | 南通星球石墨股份有限公司 | Method for removing fluorine and chlorine by sulfuric acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4206187A (en) * | 1975-12-15 | 1980-06-03 | Davy Powergas, Inc. | Process for removing sulfur dioxide from gas |
| CN102502855A (en) * | 2011-11-01 | 2012-06-20 | 大冶有色设计研究院有限公司 | Method for preparing ammonium perrhenate through extracting from coppersmelting exhaust gas washing acid pickle |
| CN102698550A (en) * | 2012-03-01 | 2012-10-03 | 南丹县吉朗铟业有限公司 | Combined foam and packing furnace gas purification tower |
| CN103288199A (en) * | 2013-06-27 | 2013-09-11 | 兰州捷晖生物环境工程有限公司 | Smelting gas acid-production wastewater treatment system |
| CN203903981U (en) * | 2014-06-12 | 2014-10-29 | 白银有色集团股份有限公司 | Fluorine and chlorine removal and recovery device used in system for making acid by using copper smelting gas |
-
2014
- 2014-06-12 CN CN201410260042.9A patent/CN104030254B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4206187A (en) * | 1975-12-15 | 1980-06-03 | Davy Powergas, Inc. | Process for removing sulfur dioxide from gas |
| CN102502855A (en) * | 2011-11-01 | 2012-06-20 | 大冶有色设计研究院有限公司 | Method for preparing ammonium perrhenate through extracting from coppersmelting exhaust gas washing acid pickle |
| CN102698550A (en) * | 2012-03-01 | 2012-10-03 | 南丹县吉朗铟业有限公司 | Combined foam and packing furnace gas purification tower |
| CN103288199A (en) * | 2013-06-27 | 2013-09-11 | 兰州捷晖生物环境工程有限公司 | Smelting gas acid-production wastewater treatment system |
| CN203903981U (en) * | 2014-06-12 | 2014-10-29 | 白银有色集团股份有限公司 | Fluorine and chlorine removal and recovery device used in system for making acid by using copper smelting gas |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105797540A (en) * | 2014-12-27 | 2016-07-27 | 江苏振方生物化学有限公司 | Method for absorbing exhaust from chlorobenzotrifluoride synthesis |
| CN106823759A (en) * | 2017-02-28 | 2017-06-13 | 中国恩菲工程技术有限公司 | Defluorinate chlorine device |
| CN114906823A (en) * | 2022-05-07 | 2022-08-16 | 南通星球石墨股份有限公司 | Method for removing fluorine and chlorine by sulfuric acid |
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| CN104030254B (en) | 2016-02-24 |
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