CN101823767B - Method for preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor - Google Patents
Method for preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor Download PDFInfo
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- CN101823767B CN101823767B CN2010101739493A CN201010173949A CN101823767B CN 101823767 B CN101823767 B CN 101823767B CN 2010101739493 A CN2010101739493 A CN 2010101739493A CN 201010173949 A CN201010173949 A CN 201010173949A CN 101823767 B CN101823767 B CN 101823767B
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Abstract
The invention discloses a method for preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor, and relates to a method for preparing powder material. The method solves the problems of high treatment cost and disguised secondary pollution to the environment of a traditional method for treating hydrochloric acid pickling wastewater which contains Fe2+. The method comprises the following steps that: air is fed into a reactor with the hydrochloric acid pickling wastewater which contains Fe2+, until the Fe2+ in the hydrochloric acid pickling wastewater is fully oxidized into Fe3+; the wastewater stays still, is cooled, and is added with dispersant and urea; ammonia is dripped into the wastewater, reaction is carried out in water bath, the wastewater stays still, and is cooled, oscillated, washed and filtered by deionized water; the deposit after filtration is dried and calcined for 2h, and the product is obtained. The method for preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor has mild reaction conditions, utilizes the pickling waste liquor which contains Fe2+ in the waste, not only prevents the pollution of the pickling waste liquor which contains Fe2+ to the environment, but also recycles iron resources, and does not produce secondary pollution.
Description
Technical field
The present invention relates to a kind of method for preparing powder body material.
Background technology
In the course of processing of steel product, often to carry out acid pickling and rust removing to its surface and handle with hydrochloric acid, produce a large amount of spent pickle liquors thus.The composition of hydrochloric acid pickling waste liquor mainly is small amount of impurities such as hydrogenchloride, iron protochloride and water.Its content is different and different with specification with acid cleaning process, service temperature, rolling shapes, and it is ferrous 10～30% generally to contain chlorination, hydrogenchloride 3～10%.Spent pickle liquor can not directly discharge by national requirements for environmental protection, and traditional treatment process is to adopt roasting to reclaim salt acid system and neutralisation.It is huge that the investment of salt acid system is reclaimed in roasting, and general enterprise can't accept.Neutralisation is the method that existing iron and steel enterprise generally adopts; But the shortcoming of its existence is also more outstanding; To consume a large amount of basic agent (like caustic soda, lime etc.) on the one hand; Processing cost is very expensive, can generate again on the other hand to be difficult to the iron containing sludge disposed in a large number, and environment is caused covert secondary pollution.How effectively disposing spent pickle liquor is extremely urgent problem.
Summary of the invention
Goal of the invention of the present invention is for the method processing cost costliness that solves existing processing spent pickle liquor, environment is caused covert secondary pollution problem, and a kind of method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor is provided.
The present invention is following with the method for preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the Fe that contains that handles through step 1
2+Hydrochloric acid pickling waste liquor in add dispersion agent, add urea again, dropping ammonia to pH value is 5.5～6.5 then; In 85 ℃ water-bath, react 4h～8h; Leave standstill cooling, again in ultrasonic cleaning machine with 70%～99% ultrasonic power vibration 5min～15min, use deionized water wash, suction filtration then; Three, the deposition of gained behind the step 2 suction filtration is dry, in 250 ℃～500 ℃ retort furnace, calcine 2h then, promptly get nano ferric oxide powder material; The dispersion agent add-on is for containing Fe in the step 2
2+Hydrochloric acid pickling waste liquor and dispersion agent gross weight 2%～5%, contain Fe in the step 2
2+Hydrochloric acid pickling waste liquor and the mass ratio of urea be 16～40 : 1, the dispersion agent described in the step 2 is Macrogol 200, PEG 400, polyoxyethylene glycol 800, Macrogol 2000, Macrogol 3000, Macrogol 4000, cetyl trimethylammonium bromide, X 2073 or sodium laurylsulfonate.
The present invention has the following advantages:
1, compare the present invention with existing preparation nano ferric oxide powder material method and under the reaction conditions of gentleness, carry out, very low to the conversion unit requirement, low to the equipment corrosion degree, preparation technology is simple.
2, the raw materials cost of the present invention's employing is cheap, utilizes the waste spent pickle liquor of industry generations such as mechanical workout, has both avoided spent pickle liquor that environment is produced and has polluted, and makes fe source be able to recycle again.
3, do not produce secondary pollution.The enterprise of present many production ferric oxide powder materials, as precipitation agent, a large amount of sodium salts in reaction back can't reclaim with inexpensive NaOH, and the post-processed cost is very expensive, can generate again to be difficult to the iron containing sludge disposed in a large number, and environment is caused covert secondary pollution.The present invention can avoid reacting the problem that the back generates sodium salt through using ammoniacal liquor as precipitation agent, is beneficial to environmental protection.
4, the red stone particle diameter of the present invention's production is controlled, can prepare different grains through using different dispersion agents
The ferric oxide powder material of sub-size.
Description of drawings
Fig. 1 is the stereoscan photograph of embodiment 11 gained nano ferric oxide powder materials; Fig. 2 is the stereoscan photograph of embodiment 11 gained nano ferric oxide powder materials; Fig. 3 is the stereoscan photograph of embodiment 11 gained nano ferric oxide powder materials; Fig. 4 is the stereoscan photograph of embodiment 20 gained nano ferric oxide powder materials; Fig. 5 is the stereoscan photograph of embodiment 21 gained nano ferric oxide powder materials.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the Fe that contains that handles through step 1
2+Hydrochloric acid pickling waste liquor in add dispersion agent, add urea again, dropping ammonia to pH value is 5.5～6.5 then; In 85 ℃ water-bath, react 4h～8h; Leave standstill cooling, again in ultrasonic cleaning machine with 70%～99% ultrasonic power vibration 5min～15min, use deionized water wash, suction filtration then; Three, the deposition of gained behind the step 2 suction filtration is dry, in 250 ℃～500 ℃ retort furnace, calcine 2h then, promptly get nano ferric oxide powder material; The dispersion agent add-on is for containing Fe in the step 2
2+Hydrochloric acid pickling waste liquor and dispersion agent gross weight 2%～5%, contain Fe in the step 2
2+Hydrochloric acid pickling waste liquor and the mass ratio of urea be 16～40 : 1, the dispersion agent described in the step 2 is Macrogol 200, PEG 400, polyoxyethylene glycol 800, Macrogol 2000, Macrogol 3000, Macrogol 4000, cetyl trimethylammonium bromide, X 2073 or sodium laurylsulfonate.
Used ultrasonic cleaning machine model is a KQ2200DB type numerical control supersonic cleanser in this embodiment, is produced by Kunshan Ultrasonic Instruments Co., Ltd..
In this embodiment step 1 according to State Standard of the People's Republic of China GB/T5750.6---2006 Central Asia iron ion content measuring methods are tested and are contained Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 164.55～300g/L; The concentration of mn ion is 0～1000mg/L; The concentration of cupric ion is 0～500mg/L; Nickel concentration is 0～1000mg/L, and the concentration of chromium ion is 0～1000mg/L, and the massfraction of HCl is 0～5%.
Embodiment two: what this embodiment and embodiment one were different is under 87 ℃ condition, to react 12h in the step 1.Other is identical with embodiment one.
Embodiment three: what this embodiment was different with one of embodiment one or two is that dropping ammonia to pH value is 6.0 in the step 2.Other is identical with one of embodiment one or two.
Embodiment four: this embodiment is different with one of embodiment one to three be in the step 2 in ultrasonic cleaning machine with 89% ultrasonic power vibration.Other is identical with one of embodiment one to three.
Embodiment five: this embodiment is different with one of embodiment one to four be in the step 2 dispersion agent add-on for containing Fe
2+Hydrochloric acid pickling waste liquor and dispersion agent gross weight 4%.Other is identical with one of embodiment one to four.
Embodiment six: what this embodiment was different with one of embodiment one to five is to contain Fe in the step 2
2+Hydrochloric acid pickling waste liquor and the mass ratio of urea be 20～30 : 1.Other is identical with one of embodiment one to five.
Embodiment seven: what this embodiment was different with one of embodiment one to five is to contain Fe in the step 2
2+Hydrochloric acid pickling waste liquor and the mass ratio of urea be 25 : 1.Other is identical with one of embodiment one to five.
Embodiment eight: what this embodiment was different with one of embodiment one to seven is in 300 ℃ retort furnace, to calcine in the step 3.Other is identical with one of embodiment one to seven.
Embodiment nine: what this embodiment was different with one of embodiment one to seven is in 350 ℃ retort furnace, to calcine in the step 3.Other is identical with one of embodiment one to seven.
Embodiment ten: what this embodiment was different with one of embodiment one to seven is in 400 ℃ retort furnace, to calcine in the step 3.Other is identical with one of embodiment one to seven.
Embodiment 11: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 5.62 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 3.42g nano ferric oxide powder material.
Find out that by Fig. 1 this embodiment gained nano ferric oxide powder material particle diameter is the dark red brown nano-sized iron oxide of double-deck reticulated structure of 20nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 164.55～300g/L; The concentration of mn ion is 0～1000mg/L; The concentration of cupric ion is 0～500mg/L; Nickel concentration is 0～1000mg/L, and the concentration of chromium ion is 0～1000mg/L, and the massfraction of HCl is 0～5%.
Embodiment 12: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml Macrogol 200 again, dropping ammonia to pH value is 6.11 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 6.93g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is globosity, the nano oxidized iron particle of dark-brown, and median size is 65nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 164.55g/L, and the concentration of mn ion is 364.5mg/L.
Embodiment 13: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add 2ml polyoxyethylene glycol 800 again, dropping ammonia to pH value is 6.48 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 4.23g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is globosity, the nano oxidized iron particle of dark-brown, and median size is 90nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 164.55g/L, and the concentration of cupric ion is 7.05mg/L.
Embodiment 14: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml Macrogol 3000 again, dropping ammonia to pH value is 5.44 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 5.74g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is globosity, the nano oxidized iron particle of dark-brown, and median size is 110nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 165g/L, and nickel concentration is 24.1mg/L.
Embodiment 15: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml Macrogol 4000 again, dropping ammonia to pH value is 6.08 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 6.13g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is globosity, the nano oxidized iron particle of dark-brown, and median size is 80nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 166g/L, and the concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Embodiment 16: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml Macrogol 2000 again, dropping ammonia to pH value is 6.08 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 5.33g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is globosity, the nano oxidized iron particle of dark-brown, and median size is 150nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 167g/L, and the concentration of mn ion is 364.5mg/L, and the concentration of cupric ion is 7.05mg/L.
Embodiment 17: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 6.38 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 4.21g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is globosity, the nano oxidized iron particle of dark-brown, and median size is 25nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 168g/L, and the concentration of cupric ion is 7.05mg/L, and the massfraction of HCl is 0.38%.
Embodiment 18: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 3g cetyl trimethylammonium bromide again, dropping ammonia to pH value is 5.49 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 5.10g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is globosity, the nano oxidized iron particle of dark-brown, and median size is 120nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 169g/L, and nickel concentration is 24.1mg/L, and the massfraction of HCl is 0.38%.
Embodiment 19: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 3g sodium laurylsulfonate again, dropping ammonia to pH value is 5.80 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 5.66g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is globosity, the nano oxidized iron particle of dark-brown, and median size is 100nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 175g/L, and the concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Embodiment 20: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 3g X 2073 again, dropping ammonia to pH value is 5.54 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 4.04g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is globosity, the nano oxidized iron particle of dark-brown, and median size is 200nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 185g/L, and the concentration of mn ion is 364.5mg/L, and the concentration of cupric ion is 7.05mg/L.
Embodiment 21: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 6.12 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 500 ℃ retort furnace, calcines 2h then, promptly gets the 3.81g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is globosity, the nano oxidized iron particle of dark-brown, and median size is 50～60nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 186g/L, and the concentration of mn ion is 364.5mg/L, and nickel concentration is 24.1mg/L, and the massfraction of HCl is 0.38%.
Embodiment 22: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 6.32 then; In 85 ℃ water-bath, react 4h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 4.81g nano ferric oxide powder material.
Get nano ferric oxide powder material through scanning electron microscope analysis and be long 350～450nm, diameter is 200～350nm fusiform RED IRON OXIDE particle.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 189g/L, and the concentration of mn ion is 364.5mg/L, and the concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Embodiment 23: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 5.51 then; In 85 ℃ water-bath, react 7h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 6.39g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is the reddish-brown red stone, is the space reticulated structure, and diameter is between 80～100nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 200g/L, and the concentration of cupric ion is 7.05mg/L, and nickel concentration is 24.1mg/L, and the concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Embodiment 24: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 6.15 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 4.92g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is that particle diameter is the reddish-brown iron oxide particles of 80nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 210g/L, and nickel concentration is 24.1mg/L, and the concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Embodiment 25: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 6.24 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 5min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 6.02g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is the reddish-brown red stone, and diameter is between 130～150nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 220g/L; The concentration of mn ion is 364.5mg/L, and the concentration of cupric ion is 7.05mg/L, and nickel concentration is 24.1mg/L; The concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Embodiment 26: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 5.77 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 10min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 4.74g nano ferric oxide powder material.
Get nano ferric oxide powder material through scanning electron microscope analysis and be long 160～280nm, diameter is a 50nm acicular structure scarlet ferric oxide particles.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 250g/L; The concentration of mn ion is 364.5mg/L, and the concentration of cupric ion is 7.05mg/L, and nickel concentration is 24.1mg/L; The concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Embodiment 27: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 5.85 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 450 ℃ retort furnace, calcines 2h then, promptly gets the 7.39g nano ferric oxide powder material.
Getting the nano ferric oxide powder material particle diameter through scanning electron microscope analysis is the red iron oxide particles of 150nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 260g/L; The concentration of mn ion is 364.5mg/L, and the concentration of cupric ion is 7.05mg/L, and nickel concentration is 24.1mg/L; The concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Embodiment 28: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 6.26 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 300 ℃ retort furnace, calcines 2h then, promptly gets the 8.02g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is club shaped structure, cherry red stone, and long is 700nm, and diameter is 200nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 290g/L; The concentration of mn ion is 364.5mg/L, and the concentration of cupric ion is 7.05mg/L, and nickel concentration is 24.1mg/L; The concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Embodiment 29: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 5.47 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 250 ℃ retort furnace, calcines 2h then, promptly gets the 8.35g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is the spherical ferric oxide particles of club shaped structure, xanchromatic oxygen, and diameter is 300nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 300g/L; The concentration of mn ion is 364.5mg/L, and the concentration of cupric ion is 7.05mg/L, and nickel concentration is 24.1mg/L; The concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Embodiment 30: the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor in this embodiment is following: one, air is fed to be equipped with and contain Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the contain Fe of 80g through the step 1 processing
2+Hydrochloric acid pickling waste liquor in add 5g urea, add the 2ml PEG 400 again, dropping ammonia to pH value is 6.05 then; In 85 ℃ water-bath, react 8h, leave standstill cooling, again in ultrasonic cleaning machine with 99% ultrasonic power vibration 15min; Pour B then into; Use deionized water wash, suction filtration obtains Fe (OH)
3Deposition; Three, with the Fe (OH) of gained behind the step 2 suction filtration
3Deposition is dry, in 350 ℃ retort furnace, calcines 2h then, promptly gets the 6.31g nano ferric oxide powder material.
Getting nano ferric oxide powder material through scanning electron microscope analysis is club shaped structure, reddish-brown disk shape ferric oxide particles, and mean diameter is 150nm.
This embodiment contains Fe
2+Hydrochloric acid pickling waste liquor in each composition and content following: the concentration of iron ion is 164.55g/L; The concentration of mn ion is 364.5mg/L, and the concentration of cupric ion is 7.05mg/L, and nickel concentration is 24.1mg/L; The concentration of chromium ion is 17.5mg/L, and the massfraction of HCl is 0.38%.
Claims (10)
1. with the method for preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor, it is characterized in that with containing Fe
2+Hydrochloric acid pickling waste liquor to prepare the method for nano ferric oxide powder material with controllable grain size following: one, air is fed to be equipped with and contains Fe
2+The reactor drum of hydrochloric acid pickling waste liquor in, under 85 ℃～90 ℃ condition, react 12h then, to containing Fe
2+Hydrochloric acid pickling waste liquor in Fe
2+All be oxidized to Fe
3+, leave standstill cooling; Two, to the Fe that contains that handles through step 1
2+Hydrochloric acid pickling waste liquor in add dispersion agent; Add urea again; Dropping ammonia to pH value is 5.5～6.5 then, in 85 ℃ water-bath, reacts 4h～8h, leaves standstill cooling; Again in ultrasonic cleaning machine with 70%～99% ultrasonic power vibration 5min～15min, use deionized water wash, suction filtration then; Three, the deposition of gained behind the step 2 suction filtration is dry, in 250 ℃～500 ℃ retort furnace, calcine 2h then, promptly get nano ferric oxide powder material; The dispersion agent add-on is for containing Fe in the step 2
2+Hydrochloric acid pickling waste liquor and dispersion agent gross weight 2%～5%, contain Fe in the step 2
2+Hydrochloric acid pickling waste liquor and the mass ratio of urea be 16～40: 1, the dispersion agent described in the step 2 is Macrogol 200, PEG 400, polyoxyethylene glycol 800, Macrogol 2000, Macrogol 3000, Macrogol 4000, cetyl trimethylammonium bromide, X 2073 or sodium laurylsulfonate; Used ultrasonic cleaning machine model is a KQ2200DB type numerical control supersonic cleanser in the step 2.
2. the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor according to claim 1 is characterized in that under 87 ℃ condition, reacting 12h in the step 1.
3. the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor according to claim 1 and 2 is characterized in that dropping ammonia to pH value is 6.0 in the step 2.
4. the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor according to claim 3 is characterized in that in the step 2 in ultrasonic cleaning machine the ultrasonic power vibration with 89%.
5. according to claim 1,2 or 4 described methods, it is characterized in that the dispersion agent add-on is for containing Fe in the step 2 with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor
2+Hydrochloric acid pickling waste liquor and dispersion agent gross weight 4%.
6. the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor according to claim 5 is characterized in that containing in the step 2 Fe
2+Hydrochloric acid pickling waste liquor and the mass ratio of urea be 20～30: 1.
7. the method with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor according to claim 5 is characterized in that containing in the step 2 Fe
2+Hydrochloric acid pickling waste liquor and the mass ratio of urea be 25: 1.
8. according to claim 1,2,4 or 6 described methods, it is characterized in that in 300 ℃ retort furnace, calcining in the step 3 with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor.
9. according to claim 1,2,4 or 6 described methods, it is characterized in that in 350 ℃ retort furnace, calcining in the step 3 with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor.
10. according to claim 1,2,4 or 6 described methods, it is characterized in that in 400 ℃ retort furnace, calcining in the step 3 with preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor.
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| CN104944665B (en) * | 2015-06-19 | 2017-04-26 | 浙江大学 | Comprehensive resourceful treatment method for chlorohydric acid pickling waste liquid |
| CN107032963A (en) * | 2017-05-18 | 2017-08-11 | 哈尔滨师范大学 | The regulation and control synthetic method of propylene glycol monomethyl ether |
| CN107673410A (en) * | 2017-10-19 | 2018-02-09 | 兰州城市学院 | The method that nano ferriferrous oxide is prepared using industrial ferrous contained waste liquid |
| CN108371938A (en) * | 2018-05-09 | 2018-08-07 | 上海大学 | Mesoporous magnetic Nano iron oxide material, preparation method and applications |
| CN117326597B (en) * | 2023-08-30 | 2024-05-24 | 宁波爱诗化妆品有限公司 | Method for regulating and controlling size of nano iron oxide yellow, nano iron oxide yellow and application thereof |
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