CN1072219A - The treatment technology of cold rolling chlorohydric acid pickling spent acid - Google Patents
The treatment technology of cold rolling chlorohydric acid pickling spent acid Download PDFInfo
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- CN1072219A CN1072219A CN91110619A CN91110619A CN1072219A CN 1072219 A CN1072219 A CN 1072219A CN 91110619 A CN91110619 A CN 91110619A CN 91110619 A CN91110619 A CN 91110619A CN 1072219 A CN1072219 A CN 1072219A
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- hydrochloric acid
- acid
- roasting
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- extraction
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to field of waste water treatment, be applicable to that steel or processing component clean the spent acid that is produced through hydrochloric acid and handle.Feature is that the iron protochloride extraction raffinate that obtains behind the extraction process separated free hydrochloric acid is further handled with roasting method, makes FeCl
22H
2The O powder, 300-400 ℃ of following roastings, furnace gas absorbs through three sections absorption systems and obtains the hydrochloric acid of regenerating, and obtains brown iron oxide simultaneously.
Description
The invention belongs to field of waste water treatment, relate in particular to the treatment process of cold rolling chlorohydric acid pickling spent acid.
Carbon steel cold rolled sheet factory consumes a large amount of hydrochloric acid and carries out pickling, and spent acid consists of generally speaking: free hydrochloric acid concentration 5-8%, and iron protochloride concentration 90-200 gram (in iron)/liter.The definition of regeneration of hydrochloric acid is the technology that the chlorine that iron protochloride in the spent acid is contained is converted into hydrochloric acid.The method of regeneration of hydrochloric acid mainly contains two kinds at present: (1) Shandong is nanofarad (Ruthner) now, i.e. spray roasting.Spent acid is given heat concentrate the back and spray into by the roasting furnace roof, the coal gas heating of directly burning in the stove, the roasting furnace body temperature is about 670 ℃, and the tail gas that obtains containing hydrogenchloride once absorbs through packing tower and obtains hydrochloric acid, obtains particulate oxidation iron at the bottom of the stoving oven.(2) Lurgi process (Lurgi), i.e. fluiddized-bed roasting method.Spent acid given spraying into the fluidized-bed that contains the ferric oxide fluidizing medium after heat concentrates, coal gas at the bottom of bed directly burning heat, 850-950 ℃ of roasting, the hydrogen chloride tail gas that obtains once absorbs through bubble-plate column and obtains hydrochloric acid.The shortcoming of above-mentioned two kinds of methods is: (1) spent acid directly sprays into roasting apparatus with liquid form, free hydrochloric acid concentration height, and high-velocity jet makes the spray gun seriously corroded under the high temperature, and stops up easily and scab.(2) maturing temperature height, roasting body of heater material corrosion is serious.(3) the hydrogenchloride furnace gas once absorbs not exclusively, and hydrogen chloride in tail gas often surpasses the permission emission standard, causes environmental pollution.
The present invention is further developing of " extraction method for treating acid wash waste liquid of rolled steel (CN88109147.2) ", and purpose is that the chlorination ferrous extraction raffinate that contains that obtains behind the extraction process separated free hydrochloric acid is further handled with roasting method, preparation regeneration hydrochloric acid and ferric oxide.
Major technique feature of the present invention is as follows: cold rolling waste hydrochloric acid separates free hydrochloric acid after extraction, and the extraction raffinate of remainder is a solution of ferrous chloride.This solution of ferrous chloride is made FeCl after evaporation concentration, crystallization, drying, pulverizing
22H
2The O powder is with FeCl
22H
2O powder form is sent into fluiddized-bed roasting, and the hydrogenchloride of generation obtains the hydrochloric acid of regenerating after absorbing, and reuses for pickling line, and roasting obtains the byproduct ferric oxide simultaneously.FeCl
22H
2The maturing temperature of O powder in fluidized-bed is 300-400 ℃, and the hydrogenchloride furnace gas that roasting produces is via the recycle acid dedusting, and condensation absorbs, and tail gas absorbs and enters atmosphere after three three sections absorption systems partly forming absorb.
What the technology that the present invention proposes was achieved in that cold rolling chlorohydric acid pickling spent acid consists of free hydrochloric acid and solution of ferrous chloride.Extract as extraction agent with tributyl phosphate-kerosene, after free hydrochloric acid is separated, obtain solution of ferrous chloride.The operational path that the present invention handles solution of ferrous chloride is as follows: solution of ferrous chloride obtains FeCl after reduction vaporization concentrates
24H
2The O crystallization, the drying dehydration makes FeCl
22H
2The O powder is sent into fluiddized-bed roasting after crushing and screening.In order to carry impurity secretly in safety and the minimizing regenerating acid, adopt the hotblast stove air-supply of indirect heating, maturing temperature is 300-400 ℃.Enter three sections absorption systems after the hydrogenchloride furnace gas process secondary cyclone dedusting that fluiddized-bed roasting obtains, three sections absorption systems are by the recycle acid dedusting, and condensation absorbs, and tail gas absorbs three parts and forms.The concentration that is obtained by condensation absorber is that the regeneration hydrochloric acid of 15-20% returns pickling line and reuses.Obtain the byproduct brown iron oxide by fluidized-bed discharge port and second stage cyclonic separator.
Advantage of the present invention is:
(1) do not have sour spray gun, do not stop up and the body of heater problem that scabs.The acid spray gun is one of stoving oven key part, makes with titanium material or other corrosion resisting alloy usually, and cost is higher, and the anacidity spray gun can be reduced investment outlay significantly.
(2) maturing temperature is lower, and with the dry powder form roasting, no a large amount of steam slows down body of heater material corrosion problem in the stove, is easy to solve.Shandong nanofarad and Lurgi process now all directly sprays into stoving oven with spent acid, merges in stove and evaporates, a series of processes such as dry and chemical reaction.The powder roasting mode that the present invention proposes only consumes chemical reaction heat in stoving oven, the thermal load of roasting apparatus is reduced, and also helps solving problem of materials.
(3) with the recycle acid dedusting, condensation absorbs, and tail gas absorbs three sections absorption system substituting disposable absorption towers, can improve the regenerating acid quality, and can eliminate the pollution of tail gas to environment effectively.
(4) be convenient to introduce the purifying link before the roasting, can control effectively or reduce foreign matter content, be convenient to produce high-quality ferrite.
Embodiment:
200,000 tons of pickling line year acid discharges of year cold rolled strip amount is 12000 cubic metres, and spent acid consists of HCl5%, the Fe(II) 130 grams per liters.The hydrochloric acid that obtains concentration after the extraction and be 8-10% returns pickling line and reuses, and contains chlorination ferrous extraction raffinate and heats outside that reduction vaporization concentrates in the natural-circulation evaporator, and concentration ratio is 2.Obtain FeCl after the cooling
24H
2Per hour 901 kilograms of O wet stocks.90-100 ℃ of dehydration down generates FeCl in vacuum rake dryer
22H
2Per hour 700 kilograms of O.After crushing and screening, obtain the FeCl that median size is 0.4-0.6mm
22H
2The O powder, send in 2.5 meters fluidized-beds of diameter 400 ℃ of following roastings, furnace gas is 20% hydrochloric acid circulation cooling and dedusting with concentration after the secondary cyclone dedusting, and heat transfer area is that 50 square metres of graphite falling film absorber condensation absorptions and 1 meter packing tower tail gas of diameter absorb.The regenerant salt acid concentration is 20%, and output is per hour 1.22 tons, and acid recovering rate is greater than 90%, and ferric oxide output is per hour 310 kilograms.The Shandong that facility investment and running maintenance expense all are lower than same scale is nanofarad and Lurgi process regeneration hydrochloric acid unit now.
Claims (1)
- A kind of cold rolling hydrochloric acid pickling waste liquor treatment technology, its waste liquid major ingredient is hydrochloric acid and iron protochloride, directly the hydrochloric acid in the waste liquid is come together in extraction agent tributyl phosphate-kerosene with extraction process, ferrous iron is retained in the aqueous extraction residue, the roasting after pervaporation, crystallization, drying, pulverizing of iron protochloride extraction raffinate obtain regenerating hydrochloric acid and brown iron oxide is characterized in that:(a) with FeCl 22H 2O powder form is sent into fluiddized-bed roasting;(b) maturing temperature is 300-400 ℃;(c) the hydrogenchloride furnace gas of fluiddized-bed roasting generation, process is by the recycle acid cooling and dedusting, and condensation absorbs, and tail gas absorbs three sections absorption systems absorptions that three parts are formed, and obtains the hydrochloric acid of regenerating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91110619A CN1025053C (en) | 1991-11-14 | 1991-11-14 | Treatment technique for waste acid of washing cold-rolled parts with chlorhydric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91110619A CN1025053C (en) | 1991-11-14 | 1991-11-14 | Treatment technique for waste acid of washing cold-rolled parts with chlorhydric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1072219A true CN1072219A (en) | 1993-05-19 |
| CN1025053C CN1025053C (en) | 1994-06-15 |
Family
ID=4910191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91110619A Expired - Fee Related CN1025053C (en) | 1991-11-14 | 1991-11-14 | Treatment technique for waste acid of washing cold-rolled parts with chlorhydric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1025053C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389078C (en) * | 2006-01-24 | 2008-05-21 | 杨淙垣 | Regeneration treatment method of steel sheet pickling waste liquor |
| CN100441527C (en) * | 2006-03-31 | 2008-12-10 | 王涛 | Treatment of acid wastewater in cold rolling neutralizing station |
| CN101367085B (en) * | 2008-05-20 | 2010-11-10 | 马鞍山钢铁股份有限公司 | Acid washing iron red desilication filter cake treating device and treating method |
| CN103771537A (en) * | 2014-01-17 | 2014-05-07 | 中国科学院过程工程研究所 | Hydrochloric acid circulation method for preparing ferrous chloride tetrahydrate, iron oxide red and sulfuric acid by using ferrous sulfate septihydrate |
| CN105174218A (en) * | 2015-10-09 | 2015-12-23 | 天津大学 | Extraction method for recovering hydrochloric acid from wastewater containing hydrochloric acid |
| CN106630334A (en) * | 2015-10-29 | 2017-05-10 | 宝山钢铁股份有限公司 | Cold-rolled acid wastewater resource and zero-emission method |
| CN107459066A (en) * | 2016-06-02 | 2017-12-12 | 嘉峪关市瑞峰精细化工有限公司 | A kind of brown iron oxide deep processing and production line |
| CN111266063A (en) * | 2020-01-23 | 2020-06-12 | 马克斯环保设备(上海)有限公司 | Heating system for acid regeneration |
| CN114162873A (en) * | 2021-12-03 | 2022-03-11 | 鞍山创鑫环保科技股份有限公司 | Method for reducing chloride ion content in iron oxide red after roasting of pickling waste liquid |
-
1991
- 1991-11-14 CN CN91110619A patent/CN1025053C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389078C (en) * | 2006-01-24 | 2008-05-21 | 杨淙垣 | Regeneration treatment method of steel sheet pickling waste liquor |
| CN100441527C (en) * | 2006-03-31 | 2008-12-10 | 王涛 | Treatment of acid wastewater in cold rolling neutralizing station |
| CN101367085B (en) * | 2008-05-20 | 2010-11-10 | 马鞍山钢铁股份有限公司 | Acid washing iron red desilication filter cake treating device and treating method |
| CN103771537A (en) * | 2014-01-17 | 2014-05-07 | 中国科学院过程工程研究所 | Hydrochloric acid circulation method for preparing ferrous chloride tetrahydrate, iron oxide red and sulfuric acid by using ferrous sulfate septihydrate |
| CN103771537B (en) * | 2014-01-17 | 2016-08-31 | 中国科学院过程工程研究所 | Ferrous sulfate heptahydrate is utilized to prepare four water ferrous chlorides, iron oxide red and the hydrochloric acid cyclic method of sulphuric acid |
| CN105174218A (en) * | 2015-10-09 | 2015-12-23 | 天津大学 | Extraction method for recovering hydrochloric acid from wastewater containing hydrochloric acid |
| CN106630334A (en) * | 2015-10-29 | 2017-05-10 | 宝山钢铁股份有限公司 | Cold-rolled acid wastewater resource and zero-emission method |
| CN107459066A (en) * | 2016-06-02 | 2017-12-12 | 嘉峪关市瑞峰精细化工有限公司 | A kind of brown iron oxide deep processing and production line |
| CN111266063A (en) * | 2020-01-23 | 2020-06-12 | 马克斯环保设备(上海)有限公司 | Heating system for acid regeneration |
| CN111266063B (en) * | 2020-01-23 | 2021-11-02 | 马克斯环保设备(上海)有限公司 | Heating system for acid regeneration |
| CN114162873A (en) * | 2021-12-03 | 2022-03-11 | 鞍山创鑫环保科技股份有限公司 | Method for reducing chloride ion content in iron oxide red after roasting of pickling waste liquid |
| CN114162873B (en) * | 2021-12-03 | 2023-12-05 | 鞍山创鑫环保科技股份有限公司 | Method for reducing chloride ion content in iron oxide red after roasting pickling waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1025053C (en) | 1994-06-15 |
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