CN103754957A - Method and device of preparing high quality ferric oxide powder by adopting chlorohydric acid pickling waste liquor - Google Patents
Method and device of preparing high quality ferric oxide powder by adopting chlorohydric acid pickling waste liquor Download PDFInfo
- Publication number
- CN103754957A CN103754957A CN201310754283.4A CN201310754283A CN103754957A CN 103754957 A CN103754957 A CN 103754957A CN 201310754283 A CN201310754283 A CN 201310754283A CN 103754957 A CN103754957 A CN 103754957A
- Authority
- CN
- China
- Prior art keywords
- spent acid
- tower
- acid
- spent
- stove
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Compounds Of Iron (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention provides method of producing high quality ferric oxide powder. A certain proportion of oxide scale is added into a dissolving tower, so that a certain proportion of Fe<3+> exists in the liquor, and the oxidizing reaction time is shortened. On the other hand, the concentration ratio is controlled, so that the total ferric concentration of silicon removing waste liquor is below 250g/L, thereby realizing the purpose of producing the high quality ferric oxide powder. The method provided by the invention has the advantages that the oxidizing reaction time can be shortened, the silicon removal effect can be improved, and the BET (Brunauer, Emmett and Teller) specific surface area of the produced ferric oxide is increased. The BET of the ferric oxide powder obtained reaches up to over 3.0, so that the high quality ferric oxide powder is produced.
Description
Technical field
The present invention relates to field of metallurgy, the technique that is specially the acid regeneration technology in metallurgical machinery, metallurgical technology and produces 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 that pickling speed is fast, the excellent feature of plate surface quality, has become a kind of main flow pickling technology in cold-rolling steel strip pickling.In waste hydrochloric acid after pickling, contain a large amount of free acids and the iron of high density, 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 need to pass through manipulation of regeneration.Regeneration of hydrochloric acid basic procedure is by the FeCl in pickle solution
2after high-temperature roasting, generate HCl and Fe
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 and 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 just better.
Silicon removing process flow process in existing technique is, spent pickle liquor enters into molten iron flask after heating from bottom, the reaction of free acid in spent pickle liquor and scrap iron, to improve the pH value of spent pickle liquor, is about 2.0 from the pH value of the spent pickle liquor of dissolving tower top overflow, spent pickle liquor is after cooling, interpolation by ammoniacal liquor in ammonia react tank adjusts to 4.0 by the pH value of solution, flow into afterwards atmospheric oxidation tank, 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+in being the solution of 4.0 left and right, pH can generate Fe (OH)
3precipitation, newly-generated Fe (OH)
3after the impurity elements such as Si, Ca in particle adsorbent solution, Mn, form solid particulate, this solid particulate is precipitated separation by the throwing out of flocculation agent in subsider, thereby obtain the pickle solution of low silicon content, with the pickle solution of low silicon content, can prepare the brown iron oxide of low silicon content.
As for the specific surface area of brown iron oxide mainly by the inner operating of stoving oven and the stove inner nozzle of stoving oven in advance to control, existing technique is produced the BET that obtains brown iron oxide and is conventionally less than 3.0, cannot meet the preparation of high-quality brown iron oxide.
Summary of the invention
The object of the invention is to propose a kind of method of producing high-quality brown iron oxide, the time that application the method can reduce oxidizing reaction on the one hand, the removal effect of raising silicon; The BET that improves on the other hand the brown iron oxide of producing, the brown iron oxide BET obtaining reaches more than 3.0, thereby realize high-quality brown iron oxide, produces.
Feature of the present invention is, the one, add a certain proportion of iron scale dissolving in tower, and make to exist in solution a certain proportion of Fe
3+, the time of minimizing oxidizing reaction, the removal effect of raising silicon; Control on the other hand concentration ratio, make total concentration of iron in silica removal waste liquid below 250g/L, thereby reach the object of production high-quality brown iron oxide.
Concrete technical scheme is: adopt the acid regeneration unit with following structure, described acid regeneration set structure comprises that the spent acid connecting successively dissolves tower, retort, flocculation reaction tank, line mixer, subsider, holding tank, thickener and spray roasting stove;
At spent acid, dissolve and on the bottom baffles of tower, place successively silicon nitride ceramic ball I and the silicon nitride ceramic ball II that diameter is 1.2～2 times of bottom baffles opening diameters and 0.8～1.0 times; 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 spray gun is installed 4～6 nozzles, and nozzle is preferably inner-rotary type nozzle.
Treatment process is, by the spent acid after pickling, sends into spent acid and dissolve tower after heating, react in spent acid dissolving tower with iron scale and iron and steel limit silk, and step comprises:
(1) on the dividing plate of spent acid dissolving tower bottom, place silicon nitride ceramic ball I, then lay successively silicon nitride ceramic ball II, limit silk layer and iron scale in the 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 70%～82% of spent acid dissolving 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 be selected the shot-peening iron scale on hot rolling iron scale or hot-rolled sheet surface;
(2) spent acid that is heated to 75～85 ℃ is sent 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 to dissolving in tower, add iron scale and iron and steel limit silk, 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); From spent acid, dissolve tower top with Bian Si and the reacted spent acid of iron scale and flow out, pH is 1.5～2.5;
(3) spent acid enters retort and carries out silica removal from dissolving top of tower and flowing out and be cooled to 35～45 ℃, 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, add ammoniacal liquor and stir neutralization from neutralization chamber top; Ammonia concn is 20wt%～30wt%, with the volume flow ratio of spent acid be 1%～2%;
Spent acid after neutralization flows into oxidation reaction chamber from neutralization chamber top, in the residence time of oxidizing chamber, be 10～20min; From oxidation reaction chamber bottom, 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, to disperse ammoniacal liquor to add the floc sedimentation of 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 adds low-molecular-weight anionic flocculant in flocculation reaction tank, 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 afterwards subsider and carries out flocculating settling; Preferably, low-molecular-weight, anionic type flocculation agent is N8173(Pulv), 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 ‰, with the volume ratio of spent acid flow be 1%～2%.
(5), after flocculating settling, collect the clear liquid that separates, and the filtrate that obtains after press filtration is processed of solid, the concentration that is concentrated into total iron ion is 210～250g/L; In concentrated solution, the concentration of total iron ion detects by online Density Measuring Instrument, once find that iron concentration exceedes the upper limit of controlling valu, is diluted by scrubber effluent;
(6) spent acid after concentrated obtains brown iron oxide at spray roasting kiln roasting; In spray roasting stove, keep negative pressure state, vacuum degree control is between-0.15～-0.25Mpa; The control of stoving oven internal temperature field requires: fire box temperature is at 685～720 ℃, 450～520 ℃ of throat temperatures, and bottom temperature is at 420～450 ℃;
Preferably, the spent acid after concentrating 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 gun head is installed 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, when improving unit processing pickling waste hydrochloric acid, solved the recycling of hot rolling iron scale, output and the quality of the unit brown iron oxide improving, therefore this technology has great promotional value, can promote in the regeneration of being transplanted to hydrochloric acid pickling waste liquor.
Employing the technology of the present invention can reduce the time of oxidizing reaction on the one hand, improves the removal effect of silicon, improves the production capacity of acid regeneration unit; Can reduce on the other hand Fe
2o
3the content of middle impurity, makes the Fe in brown iron oxide
2o
3content reaches more than 99.5%, can make especially SiO
2content lower than 60ppm; Moreover can improve Fe
2o
3bET value, guarantee that BET value reaches more than 3.0, thereby when 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 former acid regeneration 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 has been applied technology of the present invention, its device structure as shown in Figure 2, comprises that the spent acid connecting successively 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.
At spent acid, dissolve and on the bottom baffles of tower, place successively silicon nitride ceramic ball I101 and the silicon nitride ceramic ball II102 that diameter is 1.2～2 times of bottom baffles opening diameters and 0.8～1.0 times; 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.
Spray roasting stove top is connected to cyclonic separator 802; The bottom of cyclonic separator is connected with spray roasting stove bottom, and top is connected to Venturi thickener.
Retort 2 is comprised of neutralization chamber 201 and oxidation reaction chamber 202, and double-layered stirrer 203 is installed in neutralization chamber, and agitator 204 is set in ammonia neutralization district.
Concrete technology route is:
1) diameter of spent acid dissolving tower 1 is 3000mm, tower height 25100mm, the diameter that spent acid dissolves the perforate of tower bottom dividing plate is 5mm, on the dividing plate of spent acid dissolving tower bottom, place the silicon nitride ceramic ball I101 that 500mm height diameter is 10mm, laying depth is that 200mm diameter is the silicon nitride ceramic ball II102 of 5mm thereon again, on silicon nitride ceramic ball II, stack the limit silk 103 that 20000mm is high, on the silk of limit, throw in again 2000Kg iron scale 104; 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 this spent acid is heated to after 80 ℃ and squeezes into from the bottom of spent acid dissolving tower 1 through steam heater 105, 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, through Bian Si and the reacted spent acid of iron scale, from top of tower liquid stream, flowing out, pH value is 2.0 ± 0.1; Every 8 hours, from top of tower, add hot rolling iron scale 1000Kg, add limit silk 500Kg every day;
3) spent acid that tower top flows out can be selected graphite heat exchanger through interchanger 106() be cooled to 40 ℃ of left and right, enter retort 2.
Ammonia neutralization reaction and oxidizing reaction are carried out in same retort, and as shown in Figure 1, retort is comprised of neutralization chamber 201 and oxidation reaction chamber 202 structure of retort, and double-layered stirrer 203 is installed in neutralization chamber.It at the entrance of retort, is the top of neutralization chamber, by the 1.2%(volume ratio of spent acid flow) to add concentration be 20wt%～30wt% ammoniacal liquor is in spent acid, diameter at the agitator 204 in ammonia neutralization district is 300mm, the rotating speed of agitator 204 is 600rpm, from the bottom of the oxidation reaction chamber of retort, pass into the pressurized air purifying, the flow of air is 30M per hour
3, this spent pickle liquor is 20min in the residence time of retort.
4) through the reacted spent acid of silica removal, flow into flocculation reaction tank 3, and add low-molecular-weight, anionic type flocculation agent N8173(Pulv in flocculation reaction tank) (Nalco, nail (unit of length) section industrial service (Suzhou) company limited) flocculation agent;
Solution after flocculation reaction enters line mixer 4, and adding molecular weight is 30000～60000 polyacrylamide cationic flocculant.After tube mixer mixes, enter into subsider 5 sedimentations, 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 the 1.5%(volume ratio of spent acid flow).
After the precipitation extraction of flocculation, after pressure filter 6 press filtrations, filtrate is entered holding tank 701, solid otherwise processed.
5) spent pickle liquor in holding tank 701 702 carries out concentration in Venturi thickener, through online Density Measuring Instrument detect and scrubber effluent dilution after, in spent pickle liquor, always the concentration of iron ion is controlled at 220 ± 10g/L; In concentrated solution, the concentration of total iron ion detects by online Density Measuring Instrument, once find that iron concentration exceedes the upper limit of controlling valu, is diluted by scrubber effluent; The hydrogen chloride gas that solution evaporates when concentrated absorbs by pipeline separately;
6) spent pickle liquor is injected in spray roasting stove 8 by spray gun 9, and the distance between the nozzle 901 of spray gun and stove burner 801 planes is 1.3 times of stove diameter; Whole burner hearth is settled three spray guns altogether, and every gun head is installed 6 nozzles 901, and nozzle used is inner-rotary type nozzle, and this nozzle is provided by Shanghai Wu Bao Electromechanical Technology Co., Ltd.In spray roasting stove 8, keep negative pressure state, vacuum degree control between-0.20Mpa, the control requirement of stoving oven internal temperature field, fire box temperature is at 690 ± 5 ℃, 460 ± 5 ℃ of throat temperatures, bottom temperature is at 430 ± 5 ℃.
From spray roasting furnace bottom, collect brown iron oxide, the waste gas of roasting enters and separates through cyclonic separator 802 from spray roasting stove, and pressed powder is wherein got back to spray roasting stove and discharged from bottom, and gas is got back to Venturi thickener and collected hydrogen chloride gas wherein.
This unit adopts after above operational path, monthly can consume 100 tons of hot rolling iron scales, these are converted into the quality oxide iron powder of high added value originally for the iron scale of solid waste, the consumption of unit limit silk can be reduced more than 70% simultaneously, unit spent acid processing power improves more than 20%, the processing of brown iron oxide improves more than 30%, produces the Fe in the brown iron oxide obtaining
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 obtaining 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 dissolving 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.
Spray roasting stove top is connected to cyclonic separator 802a; 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 this spent acid is heated to after 80 ℃ and squeezes into from the bottom of spent acid dissolving tower 1a through steam heater 105a, 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, through Bian Si and the reacted spent acid of iron scale, from top of tower liquid stream, flowing out, pH value is 2.0 ± 0.1; Every 8 hours from top of tower limit silk 1200Kg;
The spent acid that tower top flows out can be selected graphite heat exchanger through interchanger 106() be cooled to 40 ℃ of left and right, enter neutralization chamber 201a and carry out ammonia neutralization reaction; From the top of neutralization chamber, by the 1.2%(volume ratio of spent acid flow) add the ammoniacal liquor that concentration is 20wt%～30wt%, and stirring reaction; Enter again oxidation reaction chamber 202a and carry out oxidizing reaction; From the bottom of oxidation reaction chamber, pass into the pressurized air purifying, 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, through the reacted spent acid of silica removal, flow into subsider 5a sedimentation, collect clear liquid, the waste acid liquor after sedimentation flow into spent acid holding tank 701a from subsider top.
It is the solution of 1wt ‰ that flocculating agent formulation becomes concentration, and the add-on of flocculant solution is respectively the 1.5%(volume ratio of spent acid flow).
After the precipitation extraction of flocculation, after pressure filter 6a press filtration, filtrate is entered holding tank 701a, solid otherwise processed.
Spent pickle liquor in holding tank 701a 702a in Venturi thickener carries out concentration; The hydrogen chloride gas that solution evaporates when concentrated absorbs by pipeline separately;
Spent pickle liquor is injected in spray roasting stove 8 by spray gun 9a, and the distance between the nozzle 901 of spray gun and stove burner 801 planes is 1.3 times of stove diameter; Whole burner hearth is settled three spray guns altogether, and every gun head is installed 6 nozzles 901, and nozzle used is inner-rotary type nozzle, and this nozzle is provided by Shanghai Wu Bao Electromechanical Technology Co., Ltd.In spray roasting stove 8, keep negative pressure state, vacuum degree control between-0.20Mpa, the control requirement of stoving oven internal temperature field, fire box temperature is at 690 ± 5 ℃, 460 ± 5 ℃ of throat temperatures, bottom temperature is at 430 ± 5 ℃.
The croci BET preparing by aforesaid method is less than 3, and quality is not high.And raw material used is all limit silk, cost is higher.
Claims (9)
1. a method that adopts hydrochloric acid pickling waste liquor to prepare high-quality brown iron oxide, it is characterized in that, employing has the acid regeneration unit of following structure, and described acid regeneration set structure comprises that the spent acid connecting successively 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) at spent acid, dissolve the upper silicon nitride ceramic ball I(101 that places of dividing plate (108) of tower (1) bottom), then lay successively silicon nitride ceramic ball II(102 in the above), limit silk layer (103) and iron scale (104); 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 70%～82% of spent acid dissolving 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 that is heated to 75～85 ℃ is sent into spent acid dissolving tower, and the linear velocity in tower is 1～3m/ hour, and the residence time is 6～24 hours; And to dissolving in tower, add iron scale and iron and steel limit silk, 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%; From spent acid, dissolve tower top with Bian Si and the reacted spent acid of iron scale and flow out, pH is 1.5～2.5;
(3) spent acid enters retort (2) and carries out silica removal from dissolving top of tower and flowing out and be cooled to 35～45 ℃, and retort (2) is divided into neutralization chamber (201) and oxidation reaction chamber (202); Spent acid first flows into neutralization chamber from bottom, add ammoniacal liquor and stir neutralization from neutralization chamber top; Ammonia concn is 20wt%～30wt%, with the volume flow ratio of spent acid be 1%～2%;
Spent acid after neutralization flows into oxidation reaction chamber (202) from neutralization chamber (201) top, in the residence time of oxidation reaction chamber (202), be 10～20min; From oxidation reaction chamber (202) bottom, pass into air, 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 adds low-molecular-weight anionic flocculant in flocculation reaction tank (3), to generate Fe (OH) in neutralization solution
3the electric charge on surface; Solution after flocculation reaction enters line mixer (4), in line mixer (4), adds high molecular weight polyacrylamide flocculation agent, enters afterwards subsider (5) and carries out flocculating settling;
(5) after flocculating settling, collect the clear liquid that separates, and the filtrate that obtains of solid after press filtration is processed, concentrated and be 210～250g/L by the concentration control of total iron ion;
(6) the spent acid roasting in spray roasting stove (8) after concentrated obtains brown iron oxide; In spray roasting stove (8), keep negative pressure state, vacuum degree control is between-0.15～-0.25Mpa; The control of spray roasting stove (8) internal temperature field requires: fire box temperature is at 685～720 ℃, 450～520 ℃ of throat temperatures, and bottom temperature is at 420～450 ℃.
2. 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 (1), described iron scale is selected the shot-peening iron scale on hot rolling iron scale or hot-rolled sheet surface.
3. 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 (2), after heating, spent acid is 8～18 hours at spent acid dissolving dwell time in the tower.
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 to be mixed with the polyacrylamide flocculant of high molecular the solution that concentration is 0.8wt ‰～1.5wt ‰, with the volume ratio of spent acid flow be 1%～2%.
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 concentrating 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 gun head is installed 4～6 nozzles, and nozzle used is inner-rotary type nozzle.
7. an acid regeneration unit that adopts hydrochloric acid pickling waste liquor to prepare high-quality brown iron oxide, it is characterized in that, structure comprises that the spent acid connecting successively 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);
At spent acid, dissolve on the bottom baffles (108) of tower (1) and place successively the silicon nitride ceramic ball I(101 that diameter is 1.2～2 times of bottom baffles (108) opening diameters and 0.8～1.0 times) and silicon nitride ceramic ball II(102); The entrance of spent acid is positioned at spent acid and dissolves tower (1) bottom, and spent acid dissolves top of tower (1) and is connected successively with water cooler (106), retort (2), flocculation reaction tank (3), line mixer (4), subsider (5); Subsider (5) top connects holding tank (701), and subsider (5) bottom is connected to pressure filter (6), and the liquid exit of pressure filter (6) is connected to holding tank (701); The bottom of holding tank (701) is connected successively with Venturi thickener (702), densometer (703) and spray gun (9); The nozzle (901) of spray gun (9) stretches into spray roasting stove.
8. described in claim 7, adopt hydrochloric acid pickling waste liquor to prepare the acid regeneration unit of high-quality brown iron oxide, it is characterized in that, the distance between nozzle (901) and the stove burner plane of described spray gun is 1.2～1.5 times of stove diameter.
9. described in claim 7, adopt hydrochloric acid pickling waste liquor to prepare the acid regeneration unit of high-quality brown iron oxide, it is characterized in that, spray gun (9) quantity is 2～6, and the head of every spray gun (9) is installed 4～6 nozzles (901), and described nozzle (901) is inner-rotary type nozzle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310754283.4A CN103754957B (en) | 2013-12-31 | 2013-12-31 | A kind of method adopting hydrochloric acid pickling waste liquor to prepare high-quality brown iron oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310754283.4A CN103754957B (en) | 2013-12-31 | 2013-12-31 | A kind of method adopting hydrochloric acid pickling waste liquor to prepare high-quality brown iron oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103754957A true CN103754957A (en) | 2014-04-30 |
| CN103754957B CN103754957B (en) | 2015-07-29 |
Family
ID=50522325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310754283.4A Active CN103754957B (en) | 2013-12-31 | 2013-12-31 | A kind of method adopting hydrochloric acid pickling waste liquor to prepare high-quality brown iron oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103754957B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399144A (en) * | 2015-12-15 | 2016-03-16 | 上海宝钢磁业有限公司 | Manganese removal method for high manganese steel pickling waste liquor |
| CN106044709A (en) * | 2016-06-06 | 2016-10-26 | 中冶南方工程技术有限公司 | Waste acid regeneration system and process |
| CN108083392A (en) * | 2017-12-21 | 2018-05-29 | 大连交通大学 | It is a kind of to prepare superfine iron oxide using pickle liquor and regenerate the devices and methods therefor of pickle |
| CN108439479A (en) * | 2018-04-24 | 2018-08-24 | 邯郸钢铁集团有限责任公司 | Cold-rolling pickling waste liquid prepares nanometer Fe2O3The system and method for photochemical catalyst |
| CN109205561A (en) * | 2018-09-25 | 2019-01-15 | 李晓垚 | A kind of industrial concentrating hydrochloric acid recovery method |
| CN110980814A (en) * | 2019-12-31 | 2020-04-10 | 上海宝钢磁业有限公司 | Method for preparing ferric oxide by regenerating waste acid of steel rolling mill unit |
| CN111573739A (en) * | 2020-06-09 | 2020-08-25 | 首钢集团有限公司 | Method for producing iron oxide red from high manganese steel waste acid liquid |
| CN113930753A (en) * | 2021-09-17 | 2022-01-14 | 武汉钢铁有限公司 | Agent and method for stabilizing rust layer of hot-rolled weather-resistant steel |
| CN114620770A (en) * | 2022-05-07 | 2022-06-14 | 长江师范学院 | Granulation impurity removal method for negative electrode material of spheroidal powder lithium iron oxide ion battery |
| CN114684862A (en) * | 2022-05-07 | 2022-07-01 | 长江师范学院 | Treatment method of lithium ion battery cathode material |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811792A (en) * | 2009-02-24 | 2010-08-25 | 宝山钢铁股份有限公司 | Processing method of stainless steel cold rolling pickling wastewater |
-
2013
- 2013-12-31 CN CN201310754283.4A patent/CN103754957B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811792A (en) * | 2009-02-24 | 2010-08-25 | 宝山钢铁股份有限公司 | Processing method of stainless steel cold rolling pickling wastewater |
Non-Patent Citations (1)
| Title |
|---|
| 康明等: "矿渣粉与粉煤灰对水泥收缩性能影响的实验研究", 《2007中国钢铁年会论文集》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399144A (en) * | 2015-12-15 | 2016-03-16 | 上海宝钢磁业有限公司 | Manganese removal method for high manganese steel pickling waste liquor |
| CN106044709A (en) * | 2016-06-06 | 2016-10-26 | 中冶南方工程技术有限公司 | Waste acid regeneration system and process |
| CN106044709B (en) * | 2016-06-06 | 2018-08-17 | 中冶南方工程技术有限公司 | A kind of waste acid regenerating system and technique |
| CN108083392B (en) * | 2017-12-21 | 2021-04-16 | 大连交通大学 | Device and method for preparing superfine iron oxide and regenerating pickling solution by using pickling waste liquor |
| CN108083392A (en) * | 2017-12-21 | 2018-05-29 | 大连交通大学 | It is a kind of to prepare superfine iron oxide using pickle liquor and regenerate the devices and methods therefor of pickle |
| CN108439479A (en) * | 2018-04-24 | 2018-08-24 | 邯郸钢铁集团有限责任公司 | Cold-rolling pickling waste liquid prepares nanometer Fe2O3The system and method for photochemical catalyst |
| CN109205561A (en) * | 2018-09-25 | 2019-01-15 | 李晓垚 | A kind of industrial concentrating hydrochloric acid recovery method |
| CN110980814A (en) * | 2019-12-31 | 2020-04-10 | 上海宝钢磁业有限公司 | Method for preparing ferric oxide by regenerating waste acid of steel rolling mill unit |
| CN111573739A (en) * | 2020-06-09 | 2020-08-25 | 首钢集团有限公司 | Method for producing iron oxide red from high manganese steel waste acid liquid |
| CN113930753A (en) * | 2021-09-17 | 2022-01-14 | 武汉钢铁有限公司 | Agent and method for stabilizing rust layer of hot-rolled weather-resistant steel |
| CN113930753B (en) * | 2021-09-17 | 2023-09-05 | 武汉钢铁有限公司 | Stabilizing treatment agent and method for hot-rolled weather-resistant steel rust layer |
| CN114620770A (en) * | 2022-05-07 | 2022-06-14 | 长江师范学院 | Granulation impurity removal method for negative electrode material of spheroidal powder lithium iron oxide ion battery |
| CN114684862A (en) * | 2022-05-07 | 2022-07-01 | 长江师范学院 | Treatment method of lithium ion battery cathode material |
| CN114620770B (en) * | 2022-05-07 | 2024-05-28 | 长江师范学院 | Granulating and impurity removing method for anode material of spheroidal powder ferric oxide lithium ion battery |
| CN114684862B (en) * | 2022-05-07 | 2024-05-28 | 长江师范学院 | Method for processing lithium ion battery cathode material |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103754957B (en) | 2015-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103754957B (en) | A kind of method adopting hydrochloric acid pickling waste liquor to prepare high-quality brown iron oxide | |
| Chen et al. | Desilication from titanium–vanadium slag by alkaline leaching | |
| CN102002585B (en) | Method for producing vanadium iron with stone-like coal pickle liquor | |
| CN101914678B (en) | Method for producing industry molybdenum oxide from molybdenum concentrate | |
| CN206052110U (en) | A kind of system for processing vanadium slag | |
| CN102605186A (en) | Method for producing manganese sulfate from manganese-rich slag through atmospheric pressure leaching | |
| CN101717858B (en) | Method for extracting molybdenum, nickel, vanadium and ferrum from polymetallic black-shale paragentic minerals | |
| CN102191388A (en) | Process for extracting vanadium from stone coal through two-section curing with concentrated acid | |
| CN103088208A (en) | Method for treating manganese-containing and phosphorus-containing hematite | |
| CN103818966B (en) | Large-specific surface area superfine powdery iron oxide red spray roasting method | |
| CN102086487A (en) | Vanadium slag treatment method capable of saving energy and reducing emission | |
| CN103508507A (en) | Method for removing metal ions in water by utilizing magnetically-separated steel slag tailings | |
| CN102616851A (en) | Resource recycling method for 80 ferrovanadium slag | |
| Xiong et al. | Simultaneous preparation of TiO2 and ammonium alum, and microporous SiO2 during the mineral carbonation of titanium-bearing blast furnace slag | |
| CN103833156B (en) | A kind for the treatment of process of cold rolling chlorohydric acid pickling spent acid | |
| CN104004920A (en) | Method for extracting vanadium from titanium tetrachloride refined tailings | |
| CN107236871A (en) | A kind of method for mixing vanadium slag and v-bearing steel slag pressurization vanadium extraction | |
| CN115820946A (en) | Comprehensive utilization method of steel slag | |
| CN102303908A (en) | Method for preparing high-solubility industrial molybdenum oxide | |
| CN101265522A (en) | Technique for extracting vanadium pentoxide by tunnel kiln calcification roasting | |
| CN107188292B (en) | Method for purifying arsenic-containing waste liquid by utilizing cyaniding silver extraction waste residues | |
| Liu et al. | Recovery of titanium and vanadium from titanium–vanadium slag obtained by direct reduction of titanomagnetite concentrates | |
| CN110306065A (en) | A kind of method that vanadium slag prepares ammonium metavanadate | |
| CN101705377B (en) | Method for extracting vanadium from stone coal by wet-process enrichment and pyrogenic-process conversion | |
| CN101476049B (en) | Method for removing magnesium from metallic ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |