CN103754957B - A kind of method adopting hydrochloric acid pickling waste liquor to prepare high-quality brown iron oxide - Google Patents
A kind of method adopting hydrochloric acid pickling waste liquor to prepare high-quality brown iron oxide Download PDFInfo
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Abstract
The present invention proposes a kind of method of producing high-quality brown iron oxide, adds a certain proportion of iron scale, make to there is a certain proportion of Fe in solution in dissolving tower
3+, reduce the time of oxidizing reaction; On the other hand control concentration ratio, make total concentration of iron in silica removal waste liquid at below 250g/L, thus reach the object of production high-quality brown iron oxide.The inventive method can reduce the time of oxidizing reaction on the one hand, improves the removal effect of silicon; Improve on the other hand the BET that institute produces brown iron oxide, the brown iron oxide BET obtained reaches more than 3.0, thus realizes the production of high-quality brown iron oxide.
Description
Technical field
The present invention relates to field of metallurgy, be specially the acid regeneration technology in metallurgical machinery, metallurgical technology and produce the technique of brown iron oxide.
Background technology
Pickling is the important link of one in process for producing cold rolled strip steel, the speed of pickling and effect directly have influence on the production capacity of milling train and the surface quality of cold-reduced sheet, chlorohydric acid pickling has the advantages that pickling speed is fast, plate surface quality is excellent, has become a kind of main flow pickling technology in cold-rolling steel strip pickling.Contain the iron of a large amount of free acids and high density in waste hydrochloric acid after pickling, this waste liquid directly discharges not only contaminate environment and also wastes a large amount of precious resources, and the spent pickle liquor that pickling unit produces for this reason needs to pass through manipulation of regeneration.Regeneration of hydrochloric acid basic procedure is by the FeCl in pickle solution
2hCl and Fe is generated after high-temperature roasting
2o
3, HCl generates hydrochloric acid and gets back to pickling process after water absorbs.
Fe
2o
3important industrial raw materials, common Fe
2o
3can be used as additive to use, and high-purity Fe
2o
3can be used as ferromagnetic substance, be used for making the soft magnetic materials of high-quality.Affect Fe
2o
3the principal element of quality is Fe
2o
3the content of middle impurity element and Fe
2o
3the specific surface area of powder, foreign matter content is lower, and specific surface area is higher, and the quality of brown iron oxide is better.
Silicon removing process flow process in existing technique is, spent pickle liquor enters into molten iron flask from bottom after heating, free acid in spent pickle liquor and scrap iron reaction, to improve the pH value of spent pickle liquor, be about 2.0 from the pH value of the spent pickle liquor dissolving tower top overflow, spent pickle liquor is after cooling, in ammonia react tank, by the interpolation of ammoniacal liquor, the pH value of solution is adjusted to 4.0, flow into atmospheric oxidation tank afterwards, in atmospheric oxidation tank, air fully contacts with spent pickle liquor, makes part Fe in spent pickle liquor
2+be oxidized to Fe
3+, air plays certain stirring action to spent pickle liquor simultaneously, the carrying out of accelerated oxidation reaction, Fe
3+be can generate Fe (OH) in the solution of about 4.0 at pH
3precipitation, newly-generated Fe (OH)
3solid particulate is formed after the impurity elements such as Si, Ca, Mn in granular absorption solution, this solid particulate is precipitated separation by the throwing out of flocculation agent in subsider, thus obtain the pickle solution of low silicon content, the brown iron oxide of low silicon content can be prepared with the pickle solution of low silicon content.
As for the specific surface area of brown iron oxide mainly through the stove inner nozzle of the inner operating of stoving oven and stoving oven in advance to control, existing technique produce the BET obtaining brown iron oxide and be usually less than 3.0, the preparation of high-quality brown iron oxide cannot be met.
Summary of the invention
The object of the invention is to propose a kind of method of producing high-quality brown iron oxide, application the method can reduce the time of oxidizing reaction on the one hand, improves the removal effect of silicon; Improve on the other hand the BET that institute produces brown iron oxide, the brown iron oxide BET obtained reaches more than 3.0, thus realizes the production of high-quality brown iron oxide.
Feature of the present invention is, one is add a certain proportion of iron scale in dissolving tower, makes to there is a certain proportion of Fe in solution
3+, reduce the time of oxidizing reaction, improve the removal effect of silicon; On the other hand control concentration ratio, make total concentration of iron in silica removal waste liquid at below 250g/L, thus reach the object of production high-quality brown iron oxide.
Concrete technical scheme is: adopt the acid regeneration unit with following structure, and described acid regeneration set structure comprises the spent acid connected successively and dissolves tower, retort, flocculation reaction tank, line mixer, subsider, holding tank, thickener and spray roasting stove;
The bottom baffles dissolving tower at spent acid places the silicon nitride ceramic ball I and silicon nitride ceramic ball II that diameter is bottom baffles opening diameter 1.2 ~ 2 times and 0.8 ~ 1.0 times successively; The entrance of spent acid is positioned at spent acid and dissolves tower bottom, and spent acid dissolves top of tower and is connected successively with water cooler, retort 2, flocculation reaction tank, line mixer, subsider; Subsider top connects holding tank, and subsider bottom is connected to pressure filter, and the liquid exit of pressure filter is connected to holding tank.The bottom of holding tank is connected with spray gun with densometer successively with Venturi thickener; The nozzle of spray gun stretches into spray roasting stove, and the distance between spray gun and stove burner plane is 1.2 ~ 1.5 times of stove diameter.
Preferably, the quantity of spray gun is 2 ~ 6, and the head of every root spray gun installs 4 ~ 6 nozzles, and nozzle is preferably inner-rotary type nozzle.
Treatment process is, by the spent acid after pickling, send into spent acid after heating and dissolve tower, react spent acid with iron scale and iron and steel limit silk and dissolve in tower, step comprises:
(1) silicon nitride ceramic ball I placed by the dividing plate that spent acid dissolves tower bottom, is then laying silicon nitride ceramic ball II, limit silk layer and iron scale successively above; The aspect ratio of silicon nitride ceramic ball I and silicon nitride ceramic ball II is 1:1 ~ 3:1, and height summation is that spent acid dissolves tower height degree 1% ~ 10%; Silicon nitride ceramic ball I diameter is 1.2 ~ 2 times of bottom baffles opening diameter, and the diameter of silicon nitride ceramic ball II is 0.8 ~ 1.0 times of bottom baffles opening diameter; The height of limit silk is that spent acid dissolves 70% ~ 82% of tower height degree; The ratio that the consumption of iron scale and spent acid dissolve tower volume is 10 ~ 20kg/m
3;
Described iron scale can select the shot-peening iron scale on hot rolling iron scale or hot-rolled sheet surface;
(2) spent acid being heated to 75 ~ 85 DEG C sends into spent acid dissolving tower, and the linear velocity in tower is 1 ~ 3m/ hour, and the residence time is 6 ~ 24 hours, is preferably 8 ~ 18 hours; And add iron scale and iron and steel limit silk in dissolving tower, the mass volume ratio of iron scale and iron and steel limit silk and spent acid is respectively 12 ~ 20kg/m
3with 2 ~ 3kg/m
3; Free HCl concentration in spent acid is 3% ~ 8% (wt); Dissolve tower top with Bian Si and the reacted spent acid of iron scale from spent acid to flow out, pH is 1.5 ~ 2.5;
(3) spent acid flows out from dissolving top of tower and is cooled to 35 ~ 45 DEG C and enters retort and carry out silica removal, and ammonia neutralization reacts and oxidizing reaction is carried out in a retort; Retort is divided into neutralization chamber and oxidation reaction chamber; Spent acid first flows into neutralization chamber from bottom, adds ammoniacal liquor and stir neutralization from neutralization chamber top; Ammonia concn is 20wt% ~ 30wt%, is 1% ~ 2% with the volume flow ratio of spent acid;
Spent acid after neutralization flows into oxidation reaction chamber from neutralization chamber top, is 10 ~ 20min in the residence time of oxidizing chamber; Bottom oxidation reaction chamber, pass into air, the volume flow ratio of air and spent acid is 1:2 ~ 4;
Neutralization chamber is 1 ~ 3:10 with the diameter ratio of oxidation reaction chamber; Neutralization chamber arranges pair of lamina agitator, and this agitator has strong shearing function, and rotating speed is 400 ~ 600rpm, with the floc sedimentation disperseing ammoniacal liquor to add rear formation; Oxidation reaction chamber is also provided with agitator, and the rotating speed of agitator is 100 ~ 200rpm; Spent acid residence time in retort is 15 ~ 30 minutes;
(4) spent acid after silica removal flows into flocculation reaction tank, and in flocculation reaction tank, adds low-molecular-weight anionic flocculant, to generate Fe (OH) in neutralization solution
3the electric charge on surface; Solution after flocculation reaction enters line mixer, adds high molecular weight polyacrylamide flocculation agent in line mixer, enters subsider afterwards and carries out flocculating settling; Preferably, low-molecular-weight, anionic type flocculation agent is N8173 (Pulv), and the polyacrylamide flocculant molecular weight of high molecular is 30000 ~ 60000;
Preferably, low-molecular-weight, anionic type flocculation agent and polyacrylamide flocculant are mixed with the solution that concentration is 0.8wt ‰ ~ 1.5wt ‰, are 1% ~ 2% with the volume ratio of spent acid flow.
(5), after flocculating settling, the clear liquid be separated is collected, and the filtrate that solid obtains after press filtration process, the concentration being concentrated into total iron ion is 210 ~ 250g/L; In concentrated solution, the concentration of total iron ion is detected by online Density Measuring Instrument, once find that iron concentration exceedes the upper limit of controlling valu, is then diluted by scrubber effluent;
(6) spent acid after concentrating obtains brown iron oxide at spray roasting kiln roasting; Keep negative pressure state in spray roasting stove, vacuum degree control is between-0.15 ~-0.25Mpa; The control overflow of stoving oven internal temperature field is: fire box temperature at 685 ~ 720 DEG C, throat temperature 450 ~ 520 DEG C, bottom temperature is at 420 ~ 450 DEG C;
Preferably, the spent acid after concentrated is injected in spray roasting stove by spray gun, and spray gun stretches into spray roasting stove by nozzle, and the distance between nozzle and stove burner plane is 1.2 ~ 1.5 times of stove diameter.Every root gun head installs 4 ~ 6 nozzles, and nozzle used is inner-rotary type nozzle.
The present invention proposes a kind of quality oxide PRODUCTION OF IRON POWDER technology, while raising unit process pickling waste hydrochloric acid, solve the recycling of hot rolling iron scale, the seed output and quality of the unit brown iron oxide improved, therefore this technology has great promotional value, can promote and be transplanted in the regeneration of hydrochloric acid pickling waste liquor.
Adopt the technology of the present invention can reduce the time of oxidizing reaction on the one hand, improve the removal effect of silicon, improve the production capacity of acid regeneration unit; Fe can be reduced on the other hand
2o
3the content of middle impurity, makes the Fe in brown iron oxide
2o
3content reaches more than 99.5%, can make SiO especially
2content lower than 60ppm; Moreover can Fe be improved
2o
3bET value, guarantee that BET value reaches more than 3.0, thus while utilizing hydrochloric acid pickling waste liquor to produce quality oxide iron powder, improve the processing power of the regenerating spent acid of unit.
Accompanying drawing explanation
Fig. 1 is the structural representation of oxidation tank
Fig. 2 is process unit schema of the present invention
Fig. 3 is silica removal and the ortho acid reclaiming process flow process of existing technique
1-spent acid dissolves tower, 101-silicon nitride ceramic ball I, 102-silicon nitride ceramic ball II, 103-limit silk, 104-iron scale, 105-steam heater, 106-interchanger, 108-bottom baffles, 2-retort, 201-neutralization chamber, 202-oxidation reaction chamber, 203-double-layered stirrer, 204-agitator, 3-flocculation reaction tank, 4-line mixer, 5-subsider, 6-pressure filter, 701-holding tank, 702-Venturi thickener, 703-densometer, 8-spray roasting stove, 801-burner, 802-cyclonic separator, 9-spray gun, 901-nozzle,
1a-spent acid dissolves tower, 105a-steam heater, 106a-interchanger, 201a-neutralization chamber, 202a-oxidation reaction chamber, 5a-subsider, 6a-pressure filter, 701a-holding tank, 702a-Venturi thickener, 8a-spray roasting stove, 801a-burner, 802a-cyclonic separator, 9a-spray gun, 901a-nozzle;
Embodiment
Embodiment 1
Certain acid regeneration unit applies technology of the present invention, its device structure as shown in Figure 2, comprises the spent acid connected successively and dissolves tower 1, retort 2, flocculation reaction tank 3, line mixer 4, subsider 5, pressure filter, holding tank 701, thickener 702 and spray roasting stove 8.
The bottom baffles dissolving tower at spent acid places the silicon nitride ceramic ball I 101 and silicon nitride ceramic ball II 102 that diameter is bottom baffles opening diameter 1.2 ~ 2 times and 0.8 ~ 1.0 times successively; The entrance of spent acid is positioned at spent acid and dissolves tower bottom, and spent acid dissolves top of tower and is connected successively with water cooler 106, retort 2, flocculation reaction tank 3, line mixer 4, subsider 5; Subsider top connects holding tank 701, and subsider bottom is connected to pressure filter 702, and the liquid exit of pressure filter is connected to holding tank.The bottom of holding tank is connected with spray gun with densometer successively with Venturi thickener; The nozzle 901 of spray gun stretches into spray roasting stove 8, and the distance between nozzle and stove burner plane is 1.2 ~ 1.5 times of stove diameter.
Cyclonic separator 802 is connected to above spray roasting stove; The bottom of cyclonic separator is connected with spray roasting stove bottom, and top is connected to Venturi thickener.
Retort 2 is made up of neutralization chamber 201 and oxidation reaction chamber 202, installs double-layered stirrer 203 in neutralization chamber, arranges agitator 204 in ammonia neutralization district.
Concrete technology route is:
1) spent acid dissolves the diameter of tower 1 is 3000mm, tower height 25100mm, the diameter that spent acid dissolves the perforate of tower bottom dividing plate is 5mm, the silicon nitride ceramic ball I 101 that 500mm height diameter is 10mm placed by the dividing plate of spent acid dissolving tower bottom, the silicon nitride ceramic ball II 102 of laying depth to be 200mm diameter be 5mm thereon again, silicon nitride ceramic ball II stacks the limit silk 103 that 20000mm is high, 2000Kg iron scale 104 thrown in again by limit silk; Limit silk is automobile edges of boards silks, and iron scale is hot rolling iron scale;
2) free acid concentration in unit spent acid is 5wt%, and the bottom that this spent acid dissolves tower 1 from spent acid after steam heater 105 is heated to 80 DEG C is squeezed into, and the linear velocity in tower is 1 ~ 3m/ hour, and flow is 8m per hour
3, dwell time in the tower 8 ~ 12 hours, flow out from top of tower liquid stream through Bian Si and the reacted spent acid of iron scale, pH value was 2.0 ± 0.1; Add hot rolling iron scale 1000Kg every 8 hours from top of tower, add limit silk 500Kg every day;
3) spent acid that tower top flows out is cooled to about 40 DEG C through interchanger 106 (can select graphite heat exchanger), enters retort 2.
Ammonia neutralization reaction and oxidizing reaction are carried out in same retort, and as shown in Figure 1, retort is made up of neutralization chamber 201 and oxidation reaction chamber 202 structure of retort, installs double-layered stirrer 203 in neutralization chamber.At the entrance of retort and the top of neutralization chamber, adding concentration by 1.2% (volume ratio) of spent acid flow is that the ammoniacal liquor of 20wt% ~ 30wt% is in spent acid, be 300mm at the diameter of the agitator 204 in ammonia neutralization district, the rotating speed of agitator 204 is 600rpm, pass into cleaned pressurized air from the bottom of the oxidation reaction chamber of retort, the flow of air is 30M per hour
3, this spent pickle liquor is 20min in the residence time of retort.
4) flocculation reaction tank 3 is flowed into through the reacted spent acid of silica removal, and in flocculation reaction tank, add low-molecular-weight, anionic type flocculation agent N8173 (Pulv) (Nalco, industrial service (Suzhou) company limited of nail (unit of length) section) flocculation agent;
Solution after flocculation reaction enters line mixer 4, adds the polyacrylamide cationic flocculant that molecular weight is 30000 ~ 60000.After tube mixer mixing, enter into subsider 5 sedimentation, collect clear liquid, the waste acid liquor after sedimentation flow into spent acid holding tank from subsider top.
Above-mentioned two kinds of flocculation agents are all mixed with the solution that concentration is 1wt ‰, and the add-on of flocculant solution is respectively 1.5% (volume ratio) of spent acid flow.
After the precipitation extraction of flocculation after pressure filter 6 press filtration, filtrate enters holding tank 701, solid otherwise processed.
5) spent pickle liquor in holding tank 701 702 carries out concentration in Venturi thickener, and after online Density Measuring Instrument detects and scrubber effluent is diluted, in spent pickle liquor, the concentration of total iron ion controls at 220 ± 10g/L; In concentrated solution, the concentration of total iron ion is detected by online Density Measuring Instrument, once find that iron concentration exceedes the upper limit of controlling valu, is then diluted by scrubber effluent; The hydrogen chloride gas evaporated when solution concentrates is absorbed by pipeline separately;
6) spent pickle liquor to be injected in spray roasting stove 8 by spray gun 9, and the distance between the nozzle 901 of spray gun and stove burner 801 plane is 1.3 times of stove diameter; Whole burner hearth settles three spray guns altogether, and every root gun head installs 6 nozzles 901, and nozzle used is inner-rotary type nozzle, and this nozzle is provided by Shanghai Wu Bao Electromechanical Technology Co., Ltd.Keep negative pressure state in spray roasting stove 8, vacuum degree control is between-0.20Mpa, and the control overflow of stoving oven internal temperature field, fire box temperature is at 690 ± 5 DEG C, and throat temperature 460 ± 5 DEG C, bottom temperature is at 430 ± 5 DEG C.
Collect brown iron oxide from spray roasting furnace bottom, the waste gas of roasting enters from spray roasting stove and is separated through cyclonic separator 802, and pressed powder wherein gets back to spray roasting stove from bottom discharge, and gas gets back to Venturi thickener collection hydrogen chloride gas wherein.
After this unit adopts above operational path, monthly can consume 100 tons of hot rolling iron scales, the iron scale that these scripts are solid waste is converted into the quality oxide iron powder of high added value, the consumption of unit limit silk can be reduced by more than 70% simultaneously, unit spent acid processing power improves more than 20%, the process of brown iron oxide improves more than 30%, produces the Fe in the brown iron oxide obtained
2o
3content reaches more than 99.5%, SiO
2content lower than 60ppm, Fe
2o
3bET value reach more than 3.0, the brown iron oxide obtained meets the requirement of first grade in GB/T24244-2009 completely, obtains significant economic and social benefit.
Reference examples
The device structure of prior art processes flow process as shown in Figure 3, is followed successively by steam heater 105a, spent acid dissolves tower 1a, neutralization chamber 201a, oxidation reaction chamber 202a, subsider 5a, holding tank 701a, thickener 702a and spray roasting stove 8a.
The entrance of spent acid is positioned at spent acid and dissolves tower bottom, and spent acid dissolves top of tower and is connected successively with water cooler 106a, neutralization chamber 201a, oxidation reaction chamber 202a, subsider 5a; Subsider top connects holding tank 701a, and subsider bottom is connected to pressure filter 702a, and the liquid exit of pressure filter is connected to holding tank.The bottom of holding tank is connected with spray gun successively with Venturi thickener; Spray gun stretches into spray roasting stove 8a by nozzle 901, and the distance between nozzle and stove burner 801a plane is 1.2 ~ 1.5 times of stove diameter.
Cyclonic separator 802a is connected to above spray roasting stove; The bottom of cyclonic separator is connected with spray roasting stove bottom, and top is connected to Venturi thickener.
Free acid concentration in unit spent acid is 5wt%, and the bottom that this spent acid dissolves tower 1a from spent acid after steam heater 105a is heated to 80 DEG C is squeezed into, and the linear velocity in tower is 1 ~ 3m/ hour, and flow is 8m per hour
3, dwell time in the tower 8 ~ 12 hours, flow out from top of tower liquid stream through Bian Si and the reacted spent acid of iron scale, pH value was 2.0 ± 0.1; Every 8 hours from top of tower limit silk 1200Kg;
The spent acid that tower top flows out is cooled to about 40 DEG C through interchanger 106 (can select graphite heat exchanger), enters neutralization chamber 201a and carries out ammonia neutralization reaction; From the top of neutralization chamber, add by 1.2% (volume ratio) of spent acid flow the ammoniacal liquor that concentration is 20wt% ~ 30wt%, and stirring reaction; Enter oxidation reaction chamber 202a again and carry out oxidizing reaction; Pass into cleaned pressurized air from the bottom of oxidation reaction chamber, the flow of air is 30M per hour
3, this spent pickle liquor is 20min in the residence time of retort.
In the pipeline between oxidation reaction chamber and subsider, add flocculation agent, flow into subsider 5a sedimentation through the reacted spent acid of silica removal, collect clear liquid, the waste acid liquor after sedimentation flow into spent acid holding tank 701a from subsider top.
Flocculating agent formulation becomes concentration to be the solution of 1wt ‰, and the add-on of flocculant solution is respectively 1.5% (volume ratio) of spent acid flow.
After the precipitation extraction of flocculation after pressure filter 6a press filtration, filtrate enters holding tank 701a, solid otherwise processed.
Spent pickle liquor in holding tank 701a 702a in Venturi thickener carries out concentration; The hydrogen chloride gas evaporated when solution concentrates is absorbed by pipeline separately;
Spent pickle liquor to be injected in spray roasting stove 8 by spray gun 9a, and the distance between the nozzle 901 of spray gun and stove burner 801 plane is 1.3 times of stove diameter; Whole burner hearth settles three spray guns altogether, and every root gun head installs 6 nozzles 901, and nozzle used is inner-rotary type nozzle, and this nozzle is provided by Shanghai Wu Bao Electromechanical Technology Co., Ltd.Keep negative pressure state in spray roasting stove 8, vacuum degree control is between-0.20Mpa, and the control overflow of stoving oven internal temperature field, fire box temperature is at 690 ± 5 DEG C, and throat temperature 460 ± 5 DEG C, bottom temperature is at 430 ± 5 DEG C.
The croci BET prepared by aforesaid method is less than 3, and quality is not high.And raw material used is all limit silk, cost is higher.
Claims (6)
1. the method adopting hydrochloric acid pickling waste liquor to prepare high-quality brown iron oxide, it is characterized in that, adopt the acid regeneration unit with following structure, described acid regeneration set structure comprises the spent acid connected successively and dissolves tower (1), retort (2), flocculation reaction tank (3), line mixer (4), subsider (5), holding tank (701), Venturi thickener (702) and spray roasting stove (8);
Step comprises:
(1) dissolve the dividing plate (108) upper placement silicon nitride ceramic ball I (101) of tower (1) bottom at spent acid, then lay silicon nitride ceramic ball II (102), limit silk layer (103) and iron scale (104) successively above; The aspect ratio of silicon nitride ceramic ball I and silicon nitride ceramic ball II is 1:1 ~ 3:1, and height summation is that spent acid dissolves tower height degree 1% ~ 10%; Silicon nitride ceramic ball I diameter is 1.2 ~ 2 times of bottom baffles opening diameter, and the diameter of silicon nitride ceramic ball II is 0.8 ~ 1.0 times of bottom baffles opening diameter; The height of limit silk is that spent acid dissolves 70% ~ 82% of tower height degree; The ratio that the consumption of iron scale and spent acid dissolve tower volume is 10 ~ 20kg/m
3;
(2) spent acid being heated to 75 ~ 85 DEG C sends into spent acid dissolving tower, and the linear velocity in tower is 1 ~ 3m/ hour, and the residence time is 6 ~ 24 hours; And add iron scale and iron and steel limit silk in dissolving tower, the mass volume ratio of iron scale and iron and steel limit silk and spent acid is respectively 12 ~ 20kg/m
3with 2 ~ 3kg/m
3; Free HCl mass content in spent acid is 3% ~ 8%; Dissolve tower top with Bian Si and the reacted spent acid of iron scale from spent acid to flow out, pH is 1.5 ~ 2.5;
(3) spent acid flows out from dissolving top of tower and is cooled to 35 ~ 45 DEG C and enters retort (2) and carry out silica removal, and retort (2) is divided into neutralization chamber (201) and oxidation reaction chamber (202); Spent acid first flows into neutralization chamber from bottom, adds ammoniacal liquor and stir neutralization from neutralization chamber top; Ammonia concn is 20wt% ~ 30wt%, is 1% ~ 2% with the volume flow ratio of spent acid;
Spent acid after neutralization flows into oxidation reaction chamber (202) from neutralization chamber (201) top, is 10 ~ 20min in the residence time of oxidation reaction chamber (202); Pass into air from oxidation reaction chamber (202) bottom, the volume flow ratio of air and spent acid is 1:2 ~ 4;
Neutralization chamber (201) is 1 ~ 3:10 with the diameter ratio of oxidation reaction chamber (202); Neutralization chamber (201) arranges pair of lamina agitator (203), and rotating speed is 400 ~ 600rpm; Oxidation reaction chamber is also provided with agitator (204), and the rotating speed of agitator (204) is 100 ~ 200rpm; Spent acid residence time in retort (2) is 15 ~ 30 minutes;
(4) spent acid after silica removal flows into flocculation reaction tank (3), and in flocculation reaction tank (3), adds low-molecular-weight anionic flocculant, to generate Fe (OH) in neutralization solution
3the electric charge on surface; Solution after flocculation reaction enters line mixer (4), in line mixer (4), add high molecular weight polyacrylamide flocculation agent, enters subsider (5) afterwards and carries out flocculating settling;
(5), after flocculating settling, the clear liquid be separated is collected, and the filtrate that solid obtains after press filtration process, concentrate and the concentration of total iron ion is controlled to be 210 ~ 250g/L;
(6) roasting in spray roasting stove (8) of the spent acid after concentrating obtains brown iron oxide; Keep negative pressure state in spray roasting stove (8), vacuum degree control is between-0.15 ~-0. 25MPa; The control overflow of spray roasting stove (8) internal temperature field is: fire box temperature is at 685 ~ 720 DEG C, and throat temperature 450 ~ 520 DEG C, bottom temperature is at 420 ~ 450 DEG C.
2. adopt hydrochloric acid pickling waste liquor to prepare the method for high-quality brown iron oxide described in claim 1, it is characterized in that, in step (1), the shot-peening iron scale on hot rolling iron scale or hot-rolled sheet surface selected by described iron scale.
3. adopt hydrochloric acid pickling waste liquor to prepare the method for high-quality brown iron oxide described in claim 1, it is characterized in that, in step (2), after heating, spent acid dissolves dwell time in the tower at spent acid is 8 ~ 18 hours.
4. described in claim 1, adopt hydrochloric acid pickling waste liquor to prepare the method for high-quality brown iron oxide, it is characterized in that, in step (4), described low-molecular-weight, anionic type flocculation agent is N8173, and high molecular weight polyacrylamide flocculating agent molecule amount is 30000 ~ 60000.
5. described in claim 1, adopt hydrochloric acid pickling waste liquor to prepare the method for high-quality brown iron oxide, it is characterized in that, in step (4), described low-molecular-weight, anionic type flocculation agent is be mixed with the polyacrylamide flocculant of high molecular the solution that concentration is 0.8wt ‰ ~ 1.5wt ‰, is 1% ~ 2% with the volume ratio of spent acid flow.
6. described in claim 1, adopt hydrochloric acid pickling waste liquor to prepare the method for high-quality brown iron oxide, it is characterized in that, in step (6), the spent acid after concentrated is injected in spray roasting stove by spray gun, and the distance between spray gun and stove burner plane is 1.2 ~ 1.5 times of stove diameter; Every root gun head installs 4 ~ 6 nozzles, and nozzle used is inner-rotary type nozzle.
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| CN115355515A (en) * | 2022-09-02 | 2022-11-18 | 生态环境部南京环境科学研究所 | Spray roasting process for waste acid liquor treatment |
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