CN104030254B - In copper blast furnace off-gas acid making system, fluorine chlorine removes retrieving arrangement and recovery method thereof - Google Patents
In copper blast furnace off-gas acid making system, fluorine chlorine removes retrieving arrangement and recovery method thereof Download PDFInfo
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- CN104030254B CN104030254B CN201410260042.9A CN201410260042A CN104030254B CN 104030254 B CN104030254 B CN 104030254B CN 201410260042 A CN201410260042 A CN 201410260042A CN 104030254 B CN104030254 B CN 104030254B
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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
Abstract
The present invention has carried fluorine chlorine in a kind of copper blast furnace off-gas acid making system and has removed the recovery method of retrieving arrangement, utilize sulfuric acid conversion system used heat through external heat exchanger to atmosphere temperature rising, air themperature is made to rise to 120 DEG C-180 DEG C, be sent to fluorine chlorine through gas blower and remove tower, warm air removes reverse in tower contact with Copper making spent acid at fluorine chlorine, Copper making spent acid is rapidly heated to 60 DEG C-100 DEG C, fluorine chlorine in copper blast furnace off-gas acid making system purification spent acid is separated out with the form of gas with hydrogen fluoride and hydrogenchloride, the hydrogen fluoride of separating out and hydrogenchloride enter fluorine chlorine absorption tower with warm air, absorbed in fluorine chlorine absorption tower.The present invention does not need to add the object that any medicament such as defluorinating agent and antichlor just can reach de-fluorine and chlorine removal in removal process, can reduce production cost.The fluorine chlorine recoverable that the present invention removes makes Calcium Fluoride (Fluorspan), and added value of product is comparatively large, remarkable in economical benefits, and tradition is removed fluorine and discarded by fluorine, namely causes the wasting of resources, by causing 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 of do not add any medicament analyse to the fluorine chlorinolysis completing the spent acid in copper blast furnace off-gas acid making system after by sorption complete fluorine chlorine reclaim copper blast furnace off-gas acid making system in fluorine chlorine remove retrieving arrangement and recovery method thereof.
Background technology
Fluorine in copper blast furnace off-gas and chlorine are in diluted acid purification and washing process, and fluorine and chlorine are present in purification 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.The corrodibility of hydrochloric acid to sulfate system steel pipeline is stronger.In current technique, hydrofluoric removal adds bath of glass or in dynamic wave scrubber, stack ceramic packing to complete solid fluorine.Because bath of glass viscosity is comparatively large, easily cause line clogging in course of conveying, and liquid easily froze winter, bath of glass may be caused to add.Hydrochloric acid removes without better method, by spent acid operation neutralizing treatment.This minimizing technology causes the significant wastage of resource, adds production cost.
At present, publication number is the patent of invention " defluorination method in a kind of pyrite-based sulfuric acid production " of CN101591007, adopts in pyrite-based sulfuric acid production system spent acid, to add water glass precipitated by fluorine as precipitation agent.The method is in actual production process, and in spent acid, the content of fluorine is unknown, and water glass add-on completely rule of thumb controls, and removal efficiency of flouride may be caused lower, cause the corrosion of responsibility system and device.
Summary of the invention
Technical problem to be solved by this invention provides a kind of spent acid fluorine chlorine not adding any additive to wash in the copper blast furnace off-gas acid making system purification of fluorine chlorine desorption in spent acid by physical method to remove retrieving arrangement, and the present invention also provides the recovery method of above-mentioned retrieving arrangement.
Following technical scheme is adopted for solving technical problem of the present invention:
In a kind of copper blast furnace off-gas acid making 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 and fluorine chlorine remove tower gas phase entrance and are connected, described fluorine chlorine removes middle portion in tower and loads fire resistant polypropylene Haier ring, above described fire resistant polypropylene Haier ring, spent acid acid trap is set, described spent acid acid trap is positioned at fluorine chlorine and removes tower inner 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 blast furnace off-gas acid making system, fluorine chlorine removes the recovery method of retrieving arrangement, and its step is as follows:
Spent acid in step a, copper blast furnace off-gas acid making system enters fluorine chlorine by spent acid acid trap and removes in tower, and the spent acid in copper blast furnace off-gas acid making system is evenly distributed in fire resistant polypropylene Haier ring by spent acid acid trap;
Step b, gas blower is utilized to remove toward fluorine chlorine the warm air that tower passes into 120 DEG C-180 DEG C, warm air contacts with the spent acid in the copper blast furnace off-gas acid making system in fire resistant polypropylene Haier ring is reverse, the spent acid in the copper blast furnace off-gas acid making system in fire resistant polypropylene Haier ring is made to be heated to rapidly 60 DEG C-100 DEG C, fluorine in copper blast furnace off-gas acid making system purification spent acid and chlorine are separated out with the form of gas with hydrogen fluoride and hydrogenchloride, spent acid after de-fluorine and chlorine removal returns spent acid operation, carries out neutralizing treatment;
Step c, hydrogen fluoride and hydrogenchloride remove tower gaseous phase outlet along with warm air 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 solidliquid mixture after solid-liquid separating equipment filtering separation on steps d, fluorine chlorine absorption tower is Calcium Fluoride (Fluorspan) product, and the liquid after filtering separation enters sewage disposal operation.
The present invention utilizes sulfuric acid conversion system used heat through external heat exchanger to atmosphere temperature rising, air themperature is made to rise to 120 DEG C-180 DEG C, be sent to fluorine chlorine through gas blower and remove tower, warm air removes reverse in tower contact with Copper making spent acid at fluorine chlorine, Copper making spent acid is rapidly heated to 60 DEG C-100 DEG C, fluorine chlorine in copper blast furnace off-gas acid making system purification spent acid is separated out with the form of gas with hydrogen fluoride and hydrogenchloride, the hydrogen fluoride of separating out and hydrogenchloride enter fluorine chlorine absorption tower with warm air, 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 adding calcium oxide in hydrogen fluoride absorption tower, occur to react 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 finally the Copper making spent acid of de-fluorine and chlorine removal returns spent acid operation.
In copper blast furnace off-gas acid making system provided by the invention, fluorine chlorine removes retrieving arrangement and recovery method thereof, its advantage is: 1, traditional fluorine removes needs to add medicament, to reach solid fluorine and the object except fluorine, and the present invention does not need to add in removal process the object that any medicament such as defluorinating agent and antichlor just can reach de-fluorine and chlorine removal, production cost can be reduced.2, the fluorine chlorine recoverable that the present invention removes makes Calcium Fluoride (Fluorspan), and added value of product is comparatively large, remarkable in economical benefits, and tradition is removed fluorine and discarded by fluorine, namely causes the wasting of resources, by causing environmental pollution.
Accompanying drawing explanation
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, in a kind of copper blast furnace off-gas acid making system purification spent acid, fluorine chlorine 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 entrance with fluorine chlorine and be connected, fluorine chlorine removes middle portion in tower 2 and loads fire resistant polypropylene Haier ring 6, above described fire resistant polypropylene Haier ring 6, spent acid acid trap 3 is set, spent acid acid trap 3 is positioned at fluorine chlorine and removes tower 2 inner upper, described fluorine chlorine removes tower 2 gaseous phase outlet 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, at fluorine chlorine absorption tower 4 air vout, wire mesh mist eliminator 7 is installed, go out the drop carried secretly in air.Fluorine chlorine absorption tower 4 is connected with solid-liquid separating equipment 5, because the Calcium Fluoride (Fluorspan) generated in fluorine chlorine absorption tower 4 is micro-soluble material in the solution, carries out good separating effect by solid-liquid separating equipment 5.
embodiment 1
In copper blast furnace off-gas acid making system purification spent acid, fluorine chlorine removes a recovery method for retrieving arrangement, and its step is as follows:
Step a, Copper making spent acid enter fluorine chlorine by spent acid acid trap 3 and remove in tower 2, and the spent acid in copper blast furnace off-gas acid making system is evenly distributed in fire resistant polypropylene Haier ring 6 by spent acid acid trap 3;
Step b, gas blower 1 is utilized to remove toward fluorine chlorine the warm air that tower 2 passes into 120 DEG C, warm air contacts with the spent acid in the copper blast furnace off-gas acid making system in fire resistant polypropylene Haier ring 6 is reverse, the spent acid in the copper blast furnace off-gas acid making system in fire resistant polypropylene Haier ring 6 is made to be heated to rapidly 60 DEG C-100 DEG C, fluorine in Copper making spent acid and chlorine are separated out with the form of gas with hydrogen fluoride and hydrogenchloride, spent acid after de-fluorine and chlorine removal returns spent acid operation, carries out neutralizing treatment;
Step c, hydrogen fluoride and hydrogenchloride remove tower 2 gaseous phase outlet along with warm air 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);
Solidliquid mixture solid matter after solid-liquid separating equipment 5 filtering separation on steps d, fluorine chlorine absorption tower 4 is Calcium Fluoride (Fluorspan) product; Liquid enters sewage disposal operation.
embodiment 2
In copper blast furnace off-gas acid making system purification spent acid, fluorine chlorine removes a recovery method for retrieving arrangement, and its step is as follows:
Step a, Copper making spent acid enter fluorine chlorine by spent acid acid trap 3 and remove in tower 2, and the spent acid in copper blast furnace off-gas acid making system is evenly distributed in fire resistant polypropylene Haier ring 6 by spent acid acid trap 3;
Step b, gas blower 1 is utilized to remove toward fluorine chlorine the warm air that tower 2 passes into 180 DEG C, warm air contacts with the spent acid in the copper blast furnace off-gas acid making system in fire resistant polypropylene Haier ring 6 is reverse, the spent acid in the copper blast furnace off-gas acid making system in fire resistant polypropylene Haier ring 6 is made to be heated to rapidly 60 DEG C-100 DEG C, fluorine in copper blast furnace off-gas acid making system purification spent acid and chlorine are separated out with the form of gas with hydrogen fluoride and hydrogenchloride, spent acid after de-fluorine and chlorine removal returns spent acid operation, carries out neutralizing treatment;
Step c, hydrogen fluoride and hydrogenchloride remove tower 2 gaseous phase outlet along with warm air 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);
Solidliquid mixture solid matter after solid-liquid separating equipment 5 filtering separation on steps d, fluorine chlorine absorption tower 4 is Calcium Fluoride (Fluorspan) product; Liquid enters sewage disposal operation.
Claims (3)
1. in a copper blast furnace off-gas acid making 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 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 upper, described fluorine chlorine removes tower (2) gaseous phase outlet and is connected with fluorine chlorine absorption tower (4), the absorption agent of 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 blast furnace off-gas acid making 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, arranges wire mesh mist eliminator (7) at fluorine chlorine absorption tower (4) air vout.
3. in copper blast furnace off-gas acid making 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 blast furnace off-gas acid making system purification spent acid enters fluorine chlorine by spent acid acid trap (3) and removes in tower (2), and copper blast furnace off-gas acid making system purification spent acid is evenly distributed in fire resistant polypropylene Haier ring (6) by spent acid acid trap (3);
Step b, gas blower (1) is utilized to remove the warm air that tower (2) passes into 120 DEG C-180 DEG C toward fluorine chlorine, warm air and the copper blast furnace off-gas acid making system in fire resistant polypropylene Haier ring (6) purify that spent acid is reverse to be contacted, make the copper blast furnace off-gas acid making system in fire resistant polypropylene Haier ring (6) purify spent acid and be heated to rapidly 60 DEG C-100 DEG C, fluorine in copper blast furnace off-gas acid making system purification spent acid and chlorine are separated out with the form of gas with hydrogen fluoride and hydrogenchloride, spent acid after de-fluorine and chlorine removal returns spent acid operation, carries out neutralizing treatment;
Step c, hydrogen fluoride and hydrogenchloride remove tower (2) gaseous phase outlet along with warm air 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 solidliquid mixture after solid-liquid separating equipment (5) filtering separation on steps d, fluorine chlorine absorption tower (4) is Calcium Fluoride (Fluorspan) product, and the liquid after filtering separation enters sewage disposal operation.
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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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| CN104030254B true CN104030254B (en) | 2016-02-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN114906823B (en) * | 2022-05-07 | 2023-07-14 | 南通星球石墨股份有限公司 | Method for removing fluorine and chlorine from sulfuric acid |
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| 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 |
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| 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 |
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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 |
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