CN106478084B - A kind of preparation method of magnetic iron oxide - Google Patents
A kind of preparation method of magnetic iron oxide Download PDFInfo
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- CN106478084B CN106478084B CN201610819806.2A CN201610819806A CN106478084B CN 106478084 B CN106478084 B CN 106478084B CN 201610819806 A CN201610819806 A CN 201610819806A CN 106478084 B CN106478084 B CN 106478084B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C05—FERTILISERS; MANUFACTURE THEREOF
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/00—Controlling or monitoring parameters in water treatment
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Abstract
The invention discloses a kind of preparation methods of magnetic iron oxide.1) preparation method includes the following steps: using acid acidification ferrous sulfate；2) ferrous sulfate after acidification is mixed with hydrogen peroxide and is reacted, FeOOH presoma is made；3) the FeOOH presoma and ammonium hydrogen carbonate or ammonium carbonate are subjected to neutralization reaction, obtain reaction product；4) reaction product is separated by solid-liquid separation, collects solid phase；5) solid phase is successively dried and is roasted, magnetic iron oxide is made.The magnetic iron oxide lattice defect is more, has a large amount of active binding site, and have big specific surface area, and then adsorption capacity is strong, can be widely used for sewage treatment and field of gas purification.
Description
Technical field
The invention belongs to sewage treatment and technical field of desulfuration purification, and in particular to a kind of preparation side of magnetic iron oxide
Method.
Background technique
In sewage treatment and technical field of desulfuration purification, often need in the impurity or sulphur-containing substance in reagent removing sewage
Sulphur, and then achieve the purpose that purify sewage and sulphur-containing substance.In particular, contain more sulphur-containing substance in coal or petroleum,
Hydrogen sulfide can be discharged during preparing industrial chemicals using it, is directly resulted in subsequent production workshop section in catalyst activity substance
Poison inactivation.In order to avoid there is the above problem, the prior art would generally be using the vulcanization discharged in the desulfurizing agent removing above process
Hydrogen.
In order to preferably realize the removing of hydrogen sulfide, researcher has probed into composition and structure of desulfurizing agent etc. to hydrogen sulfide
The influence of removal effect, and miscellaneous desulfurizing agent has been made.Existing desulfurizing agent obtained is mostly with Fe-series desulfurizing agent, Mn oxide
Based on desulfurizing agent, solid base/liquid base desulfurizing agent, activated carbon desulphurization agent or molecular sieve carried active metal.Wherein, iron series are de-
Sulphur agent is more traditional one of desulfurizing agent, and the type desulfurizing agent is mainly the active component using ferriferous oxide as desulfurizing agent,
The ferriferous oxide includes ferroso-ferric oxide, di-iron trioxide and hydrated ferric oxide, and the desulfurizing agent master in Fe-series desulfurizing agent
Active component majority includes two kinds or three kinds in above-mentioned ferriferous oxide.Further, researcher has found Fe-series desulfurizing agent
There is close to contact between preparation method for composition and structure etc., and different preparation methods will be obtained with different crystal forms
With the Fe-series desulfurizing agent of pattern.
For example, Chinese patent literature CN 101585557A discloses a kind of magnetic iron oxide preparation method and its obtained
Magnetic iron oxide desulfurizing agent.1) preparation method includes the following steps: solid solubility ferrous salt and solid hydroxide,
It is mixed by iron with molar ratio hydroxy for 1:2-1:3；2) mixture obtained by step 1) is completed to react by kneading,
In the kneading process, control temperature of charge is no more than 70 DEG C；3) reaction product obtained by step 2) is dried in air；4) will
Step 3) resulting material is washed and is filtered；5) step 4) resulting material is spontaneously dried or is dried；6) by step 5) products therefrom
It is roasted in 150-500 DEG C.The magnetic iron oxide as made from the above method is Fe21.333O32, after tested, this is magnetic oxygenated
The Sulfur capacity of iron desulfurizing agent reaches 62.0%.
Above-mentioned technology obtains mixture, and to mixing by mixing solid solubility ferrous salt with solid hydroxide
Material carries out kneading and completes reaction, and in kneading process, control temperature of charge is no more than 70 DEG C, and the oxidation of oxygen is made through the air
With, mixture is finally oxidized to unformed FeOOH, but entire oxidation process progress is gentle, time-consuming, oxidation is fast
Rate is slower, and crystal grain is gradually grown up, and ultimately forms the FeOOH with crystal form, to cause crystal defect to reduce, active sites
Point is reduced, specific surface area reduces, and physical absorption ability and chemical adsorption capacity accordingly decline, and is eventually led to obtained after being fired
The crystal defect of magnetic iron oxide is few, specific surface area decline, and the active site in conjunction with element sulphur is few.
Summary of the invention
For this purpose, to be solved by this invention is the defect that active site is few in magnetic iron oxide, specific surface area is small, Jin Erti
For a kind of short preparation period, active site is more, γ-Fe of large specific surface area2O3Preparation method.
γ-Fe provided by the present invention2O3Preparation method, include the following steps:
1) using acid acidification ferrous sulfate；
2) ferrous sulfate after acidification is mixed with hydrogen peroxide and is reacted, FeOOH presoma is made；
3) the FeOOH presoma and ammonium hydrogen carbonate or ammonium carbonate are subjected to neutralization reaction, obtain reaction product；
4) reaction product is separated by solid-liquid separation, collects solid phase；
5) solid phase is successively dried and is roasted, γ-Fe is made2O3。
Further, in step 1), the molar ratio of the ferrous sulfate and the acid is 1:(0.25~0.4)；
Further, in step 2), the molar ratio of the ferrous sulfate and the hydrogen peroxide is 1:(0.55~0.7)；
The temperature of the reaction step is 20-30 DEG C.
Further, the molar ratio of the FeOOH presoma and the ammonium hydrogen carbonate or the ammonium carbonate is 1:
(5-7)；
The temperature of the neutralization reaction step is 25-50 DEG C.
Further, the temperature of the drying steps is no more than 100 DEG C, and the temperature of the calcination steps is 350~450
℃。
Further, in step 1), the acid is sulfuric acid；
The ferrous sulfate is to exist in the form of the aqueous solution of solid sulphuric acid ferrous iron or ferrous sulfate.
Further, the concentration of the sulfuric acid is 60wt%~98wt%；
Ferrous sulfate content is in 90wt% or more in the aqueous solution of the ferrous sulfate.
Further, in step 2), the concentration of the hydrogen peroxide is 30~50wt%.
It further, further include the gained liquid phase and the washing solid phase after collecting the separation of solid and liquid in step 5)
Water lotion afterwards, and the liquid phase and the water lotion are evaporated up to ammonium sulfate；
In step 5), the drying is spray drying.
Further, the spray drying is the slurry for using water that the solid phase is made into concentration as 10wt%~20wt%
Liquid, and it is dry at≤100 DEG C.
Compared with prior art, the invention has the following beneficial effects:
1) preparation method of magnetic iron oxide provided by the embodiment of the present invention is quickly aoxidized ferrous iron using hydrogen peroxide
At ferric iron, in conjunction with neutralization reaction, FeOOH presoma is made, followed by dry FeOOH presoma,
Amorphous FeOOH is made, in above process, quickly oxidation and neutralization reaction can quick release it is largely hot, quickly
The thermal conductivity of release causes the defect of the amorphous FeOOH obtained after FeOOH presoma (patina) and drying more, into
And the magnetic iron oxide crystal defect that causes it to obtain after drying and roasting is also more, these defects eventually become active bound site
Point improves the working sulfur capacity of magnetic iron oxide；Furthermore quickly oxidation and neutralization reaction also shorten the system of magnetic iron oxide
The standby period；Lead to above-mentioned quick oxidation, neutralization and drying simultaneously, it is ensured that obtain amorphous FeOOH, avoid generating remaining
The FeOOH of crystal phase or other oxide crystal phases of iron；Finally amorphous FeOOH is roasted and obtains magnetic
Property iron oxide；
It is tested by XRD, it is known that final magnetic iron oxide obtained is with γ-Fe2O3Form exist, and from XRD diagram
γ-Fe can be observed in spectrum2O3Peak shape it is relatively slow, similar steamed bun peak shows γ-Fe2O3Crystallization degree is poor, crystal particle diameter is small, shape
Tend to regular shape, further demonstrates that it with biggish specific surface area and more point defect.
2) preparation method of magnetic iron oxide provided by the embodiment of the present invention, by FeOOH presoma temperature not
More than 100 DEG C, maturing temperature ensure that magnetic iron oxide is with γ-Fe at 350~450 DEG C2O3Form exist, the γ-
Fe2O3Not only there is a large amount of active binding site, and there is big specific surface area.
3) preparation method of magnetic iron oxide provided by the embodiment of the present invention is acidified ferrous sulfate using acid, is being acidified
In the process, the molar ratio of strict control ferrous sulfate and acid is in 1:(0.25~0.4) between；Then by the ferrous sulfate after acidification
It is reacted with hydrogen peroxide mixing, FeOOH presoma is made, and the molar ratio for controlling ferrous sulfate and hydrogen peroxide is 1:
Then FeOOH presoma and ammonium hydrogen carbonate or ammonium carbonate are directly carried out neutralization reaction, are reacted by (0.55~0.7)
Product, reaction product are separated by solid-liquid separation, and collect solid phase, while also collecting liquid phase, liquid phase has just obtained ammonium sulfate after being evaporated；Solid phase
Magnetic iron oxide has just been made after dry and roasting, by above-mentioned preparation method, has reduced the additive amount of acid and hydrogen peroxide, avoids
Excessive acid is reacted with raw material, improves the raw material availability of ammonium hydrogen carbonate or ammonium carbonate, also avoid excessive hydrogen peroxide with
Ammonium hydrogen carbonate or ammonium carbonate reaction generate percarbonic acid hydrogen ammonium or percarbonic acid ammonium, and then influence the purity of ammonium sulfate.Meanwhile it is sour and double
The reduction of oxygen water additive amount also reduces cost of material.
4) preparation method of magnetic iron oxide provided by the embodiment of the present invention, during the preparation process without to entire reaction
The pH value of system is regulated and controled, simple easily operated, while directly having recycled the ammonium sulfate of high-purity, can be used as agricultural fertilizer, nothing
Need subsequent cumbersome ammonium sulfate recycling step；Magnetic iron oxide obtained can be widely used for sewage treatment and field of gas purification.
Detailed description of the invention
In order to illustrate more clearly of the technical solution in the specific embodiment of the invention, specific embodiment will be retouched below
Attached drawing needed in stating is briefly described, it should be apparent that, the accompanying drawings in the following description is some realities of the invention
Mode is applied, it for those of ordinary skill in the art, without creative efforts, can also be attached according to these
Figure obtains other attached drawings.
Fig. 1 is γ-Fe made from the embodiment of the present invention 12O3X-ray diffractogram.
Specific embodiment
Purposes, technical schemes and advantages in order to better illustrate the present invention, below in conjunction with specific embodiment to this hair
It is bright to be described further.The present invention can be embodied in many different forms, and should not be construed as limited to set forth herein
Embodiment.On the contrary, providing these embodiments, so that the disclosure will be thorough and complete, and design of the invention will be filled
Divide and be communicated to those skilled in the art, the present invention will only be defined by the appended claims.
Embodiment 1
The present embodiment provides a kind of preparation methods of magnetic iron oxide, include the following steps:
1) sulfuric acid that concentration is 60wt% is added into ferrous sulfate heptahydrate solid, stirs evenly, is acidified it sufficiently,
In, the molar ratio of ferrous sulfate and sulfuric acid is 1:0.25；
2) ferrous sulfate after acidification is mixed at 20 DEG C with the hydrogen peroxide that concentration is 50wt% and reacts 0.5h, hydroxyl is made
Base iron oxide presoma, wherein the molar ratio of the ferrous sulfate and the hydrogen peroxide is 1:0.7；
It 3) is in molar ratio that 1:5 carries out neutralization reaction at 25 DEG C by the FeOOH presoma and ammonium hydrogen carbonate
0.5h obtains reaction product；
4) reaction product is separated by solid-liquid separation, collects solid phase and liquid phase respectively, the liquid phase is evaporated up to sulphur
Sour ammonium washes the solid phase；
5) first by the solid phase after washing be made into concentration be 20wt% slurries, then by the slurries at 100 DEG C into
Row spray drying, is made FeOOH, the FeOOH is roasted 1.5h at 350 DEG C, and magnetic iron oxide is made.
After measured, the specific surface area of above-mentioned magnetic iron oxide is 270m2/g。
It carries out works to above-mentioned magnetic iron oxide using X-ray diffractometer mutually to test, corresponding XRD spectrum such as Fig. 1 institute
Show, from Fig. 1 it can be seen that: magnetic iron oxide is with γ-Fe2O3Form exist, and γ-Fe can be observed from XRD spectrum2O3
Peak shape it is relatively slow, similar steamed bun peak shows γ-Fe2O3Crystallization degree is poor, crystal particle diameter is small, shape tends to regular shape, into one
Step shows it with biggish specific surface area and point defect.
After measured, the content of ammonium sulfate reaches 97wt% in by-product.
Embodiment 2
The preparation method for present embodiments providing a kind of magnetic iron oxide, includes the following steps:
1) sulfuric acid that concentration is 70wt% is added into ferrous sulfate heptahydrate solid, stirs evenly, is acidified it sufficiently,
In, the molar ratio of ferrous sulfate and sulfuric acid is 1:0.4；
2) ferrous sulfate after acidification is mixed at 30 DEG C with the hydrogen peroxide that concentration is 40wt% and reacts 1h, hydroxyl is made
Iron oxide presoma, wherein the molar ratio of the ferrous sulfate and the hydrogen peroxide is 1:0.6；
It 3) is in molar ratio that 1:7 carries out neutralization reaction 1h at 50 DEG C by the FeOOH presoma and ammonium carbonate,
Obtain reaction product；
4) reaction product is separated by solid-liquid separation, collects solid phase and liquid phase respectively, the liquid phase is evaporated up to sulphur
Sour ammonium washes the solid phase；
5) solid phase after washing is first made into the slurries that concentration is 10wt%, then carries out the slurries at 80 DEG C
Spray drying is made FeOOH, the FeOOH is roasted 2.5h at 400 DEG C, and magnetic iron oxide is made.
It carries out works to above-mentioned magnetic iron oxide using X-ray diffractometer mutually to test, magnetic iron oxide is with γ-Fe2O3
Form exist.
After measured, the specific surface area of magnetic iron oxide obtained in the present embodiment is 260m2/g。
After measured, the content of ammonium sulfate reaches 96wt% in by-product.
Embodiment 3
The present embodiment provides a kind of preparation methods of magnetic iron oxide, include the following steps:
1) sulfuric acid that concentration is 80wt% is added into ferrous sulfate heptahydrate solid, stirs evenly, is acidified it sufficiently,
In, the molar ratio of ferrous sulfate and sulfuric acid is 1:0.3；
2) ferrous sulfate after acidification is mixed at 25 DEG C with the hydrogen peroxide that concentration is 30wt% and reacts 1.5h, hydroxyl is made
Base iron oxide presoma, wherein the molar ratio of the ferrous sulfate and the hydrogen peroxide is 1:0.55；
It 3) is in molar ratio that 1:5 carries out neutralization reaction at 25 DEG C by the FeOOH presoma and ammonium hydrogen carbonate
1.5h obtains reaction product；
4) reaction product is separated by solid-liquid separation, collects solid phase and liquid phase respectively, the liquid phase is evaporated up to sulphur
Sour ammonium washes the solid phase；
5) solid phase after washing is first made into the slurries that concentration is 20wt%, then carries out the slurries at 70 DEG C
Spray drying is made FeOOH, the FeOOH is roasted 3h at 450 DEG C, and magnetic iron oxide is made.
It carries out works to above-mentioned magnetic iron oxide using X-ray diffractometer mutually to test, magnetic iron oxide is with γ-Fe2O3
Form exist.
After measured, the specific surface area of magnetic iron oxide obtained in the present embodiment is 265m2/g。
After measured, the content of ammonium sulfate reaches 95wt% in by-product.
Embodiment 4
The present embodiment provides a kind of preparation methods of magnetic iron oxide, include the following steps:
1) sulfuric acid that concentration is 90wt% is added in the aqueous solution for the ferrous sulfate for being 91wt% to concentration, stirs evenly,
It is acidified it sufficiently, wherein the molar ratio of ferrous sulfate and sulfuric acid is 1:0.35；
2) ferrous sulfate after acidification is mixed at 30 DEG C with the hydrogen peroxide that concentration is 50wt% and reacts 2h, hydroxyl is made
Iron oxide presoma, wherein the molar ratio of the ferrous sulfate and the hydrogen peroxide is 1:0.65；
It 3) is in molar ratio that 1:6 carries out neutralization reaction at 40 DEG C by the FeOOH presoma and ammonium hydrogen carbonate
2h obtains reaction product；
4) reaction product is separated by solid-liquid separation, collects solid phase and liquid phase respectively, the liquid phase is evaporated up to sulphur
Sour ammonium washes the solid phase；
5) solid phase is first made into the slurries that concentration is 15wt%, is then done the slurries by spraying at 60 DEG C
It is dry, the FeOOH is roasted into 3.5h at 420 DEG C, magnetic iron oxide is made.
It carries out works to above-mentioned magnetic iron oxide using X-ray diffractometer mutually to test, magnetic iron oxide is with γ-Fe2O3
Form exist.
After measured, the specific surface area of magnetic iron oxide obtained in the present embodiment is 270m2/g。
After measured, the content of ammonium sulfate reaches 96wt% in by-product.
Comparative example 1
This comparative example provides a kind of preparation method of magnetic iron oxide, includes the following steps:
1) sulfuric acid that concentration is 60wt% is added into ferrous sulfate heptahydrate solid, stirs evenly, is acidified it sufficiently,
In, the molar ratio of ferrous sulfate and sulfuric acid is 1:0.7；
2) ferrous sulfate after acidification is mixed at 20 DEG C with the hydrogen peroxide that concentration is 50wt% and reacts 1h, hydroxyl is made
Iron oxide presoma, wherein the molar ratio of the ferrous sulfate and the hydrogen peroxide is 1:0.8；
It 3) is in molar ratio that 1:5 carries out neutralization reaction at 25 DEG C by the FeOOH presoma and ammonium hydrogen carbonate
1h obtains reaction product；
4) reaction product is separated by solid-liquid separation, collects solid phase and liquid phase respectively, the liquid phase is evaporated up to sulphur
Sour ammonium washes the solid phase；
5) first by the solid phase after washing be made into concentration be 20wt% slurries, then by the slurries at 100 DEG C into
Row spray drying, is made FeOOH, the FeOOH is roasted 2h at 350 DEG C, and magnetic iron oxide is made.
After measured, the specific surface area of magnetic iron oxide obtained in the present embodiment is 240m2/g。
After measured, the content of ammonium sulfate reaches 82wt% in by-product.
Comparative example 2
This comparative example provides a kind of preparation method of magnetic iron oxide, includes the following steps:
1) sulfuric acid that concentration is 60wt% is added into ferrous sulfate heptahydrate solid, stirs evenly, is acidified it sufficiently,
In, the molar ratio of ferrous sulfate and sulfuric acid is 1:0.5；
2) ferrous sulfate after acidification is mixed at 20 DEG C with the hydrogen peroxide that concentration is 50wt% and reacts 1.5h, hydroxyl is made
Base iron oxide presoma, wherein the molar ratio of the ferrous sulfate and the hydrogen peroxide is 1:1；
It 3) is in molar ratio that 1:5 carries out neutralization reaction at 25 DEG C by the FeOOH presoma and ammonium hydrogen carbonate
1.5h obtains reaction product；
4) reaction product is separated by solid-liquid separation, collects solid phase and liquid phase respectively, the liquid phase is evaporated up to sulphur
Sour ammonium washes the solid phase；
5) solid phase described after washing is first made into the slurries that concentration is 20wt%, then carries out the slurries at 100 DEG C
Spray drying is made FeOOH, the FeOOH is roasted 2h at 350 DEG C, and magnetic iron oxide is made.
After measured, the specific surface area of magnetic iron oxide obtained in the present embodiment is 250m2/g。
After measured, the content of ammonium sulfate reaches 83wt% in by-product.
Comparative example 3
This comparative example provides a kind of preparation method of magnetic iron oxide comprising following steps:
1) it weighs technical grade ferrous sulfate heptahydrate and is dissolved in water, configuration obtains the sulfuric acid that molar concentration is 1.7mol/L
Ferrous iron solution；
2) sulfuric acid that concentration is 27wt% is added into ferrous sulfate solution described in step 1), controls the sulfuric acid and sulfuric acid
Ferrous molar ratio is 0.5:1, the ferrous sulfate solution being acidified；
3) under agitation, use plunger pump be added into the ferrous sulfate solution of acidification described in step 2) concentration for
The hydrogen peroxide of 40wt%, the pumping hole of the plunger pump reach liquid level or less and control the molar ratio of the hydrogen peroxide and ferrous sulfate
For 0.75:1, it is 500mL/h that speed, which is added, in control, sufficiently reacts, makes sulfuric acid, sufficiently reacts, makes ferrous sulfate complete oxidation
Ferric sulfate obtains ferrum sulfuricum oxydatum solutum；
4) technical grade ammonium hydrogencarbonate is added into the ferrum sulfuricum oxydatum solutum described in step 3), control pH value is 7, and precipitating is complete
After carry out ageing 1h, control reaction temperature is 30 DEG C, and washed later, 50 DEG C of dry 5h are to get the amorphous hydroxyl oxidation
The FeOOH is roasted 2.5h at 350 DEG C by iron, and magnetic iron oxide is made.It is collected simultaneously cleaning solution, after drying,
Obtain ammonium sulfate.
After measured, the content of ammonium sulfate is 75wt% in by-product.
Comparative example 4
This comparative example provides a kind of preparation method of magnetic iron oxide, includes the following steps: ferrous sulfate powder 1)
With solid sodium hydroxide, mixed by iron with molar ratio hydroxy for 1:3；
2) mixture obtained by step 1) is completed to react by kneading, in the kneading process, control temperature of charge is not
More than 70 DEG C；
3) reaction product obtained by step 2) is dried in air；
4) step 3) resulting material is washed and is filtered；
5) step 4) resulting material is dried to 2h at 90 DEG C；
6) by step 5) products therefrom in 400 DEG C of roasting 2h.
The magnetic iron oxide as made from the above method is Fe21.333O32.After measured, the specific surface of above-mentioned magnetic iron oxide
Product is 110m2/g。
Comparative example 5
This comparative example provides a kind of preparation method of magnetic iron oxide, includes the following steps:
1) sulfuric acid that concentration is 60wt% is added into ferrous sulfate heptahydrate solid, stirs evenly, is acidified it sufficiently,
In, the molar ratio of ferrous sulfate and sulfuric acid is 1:0.25；
2) air is passed through into the ferrous sulfate after acidification to be aoxidized, and control the oxygen in air and ferrous sulfate
Molar ratio is 0.7:1, and FeOOH presoma is made；
It 3) is in molar ratio that 1:5 carries out neutralization reaction at 25 DEG C by the FeOOH presoma and ammonium hydrogen carbonate
2h obtains reaction product；
4) reaction product is separated by solid-liquid separation, collects solid phase and liquid phase respectively, the liquid phase is evaporated up to sulphur
Sour ammonium washes the solid phase；
5) first by the solid phase after washing be made into concentration be 20wt% slurries, then by the slurries at 100 DEG C into
Row spray drying, is made FeOOH, the FeOOH is roasted 3h at 350 DEG C, and magnetic iron oxide is made.
After measured, the specific surface area of above-mentioned magnetic iron oxide is 100m2/g。
After measured, the content of ammonium sulfate reaches 82wt% in by-product.
Experimental example 1
The working sulfur capacity of magnetic iron oxide obtained in the various embodiments described above and comparative example is tested, corresponding test method is such as
Under: above-mentioned magnetic iron oxide is pulverized, filters out 80~160 mesh samples, and with the gaseous mixture of hydrogen sulfide and nitrogen, wherein
The volume fraction of hydrogen sulfide is 4%, and nitrogen is as carrier gas, and test temperature is 25 DEG C, air speed 350h-1, desulfurizing agent loadings are
10000g, fixed bed ratio of height to diameter be 3.5, can autogamy silver nitrate solution to outlet sulphur detect, test its working sulfur capacity, accordingly
Test result is as follows shown in table 1:
Table 1
| Working sulfur capacity | |
| Embodiment 1 | 70% |
| Embodiment 2 | 66% |
| Embodiment 3 | 67% |
| Embodiment 4 | 64% |
| Comparative example 1 | 55% |
| Comparative example 2 | 54% |
| Comparative example 3 | 56% |
| Comparative example 4 | 48% |
| Comparative example 5 | 43% |
From upper table 1 it can be seen that: compared with comparative example, using magnetic iron oxide made from technique of the present invention have height
Working sulfur capacity, this is because of its big specific surface area and more active binding sites.
Experimental example 2
Magnetic iron oxide obtained in the various embodiments described above and comparative example is tested to the processing capacity of sewage, with certain papermaking enterprise
The secondary clarifier effluent of industry is sewage object, carries out waste water using magnetic iron oxide made from 1-4 of the embodiment of the present invention and comparative example
Processing, water treatment efficiency are as shown in table 2.
Table 2
It is learnt from table 2, magnetic iron oxide obtained can significantly reduce COD value in sewage in the embodiment of the present invention, with comparison
Magnetic iron oxide obtained by example is compared, and the COD value of water outlet can be significantly reduced, this shows using technique system of the present invention
The magnetic iron oxide obtained has stronger oxidability and adsorption capacity, and acid and dioxygen used in technique of the present invention
The amount of water obviously lowers, and has not only saved cost of material, while reducing the impurity level in by-product, improves the pure of by-product
Degree.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of γ-Fe2O3Preparation method, include the following steps:
1) concentration is used to be acidified ferrous sulfate, mole of the ferrous sulfate and the sulfuric acid for the sulfuric acid of 60wt%~98wt%
Than for 1:(0.25~0.4)；
2) ferrous sulfate after acidification is mixed with hydrogen peroxide and is reacted, FeOOH presoma is made, the sulfuric acid is sub-
The molar ratio of iron and the hydrogen peroxide is 1:(0.55~0.7)；
3) the FeOOH presoma and ammonium hydrogen carbonate or ammonium carbonate are subjected to neutralization reaction, obtain reaction product；
4) reaction product is separated by solid-liquid separation, collects solid phase；
5) solid phase is successively dried and is roasted, γ-Fe is made2O3。
2. preparation method according to claim 1, which is characterized in that in step 2), the temperature of the reaction step is 20-
30℃。
3. preparation method according to claim 1 or 2, which is characterized in that the FeOOH presoma and the carbon
The molar ratio of sour hydrogen ammonium or the ammonium carbonate is 1:(5-7)；
The temperature of the neutralization reaction step is 25-50 DEG C.
4. preparation method according to claim 1 or 2, which is characterized in that the temperature of the drying steps is no more than 100
DEG C, the temperature of the calcination steps is 350~450 DEG C.
5. preparation method according to claim 1 or 2, which is characterized in that in step 1),
The ferrous sulfate is to exist in the form of the aqueous solution of solid sulphuric acid ferrous iron or ferrous sulfate.
6. preparation method according to claim 5, which is characterized in that ferrous sulfate contains in the aqueous solution of the ferrous sulfate
Amount is in 90wt% or more.
7. preparation method according to claim 1 or 2, which is characterized in that in step 2), the concentration of the hydrogen peroxide is 30
~50wt%.
8. preparation method according to claim 7, which is characterized in that further include collecting the separation of solid and liquid in step 5)
The water lotion after gained liquid phase and the washing solid phase afterwards, and the liquid phase and the water lotion are evaporated up to sulfuric acid
Ammonium；
In step 5), the drying is spray drying.
9. preparation method according to claim 8, which is characterized in that the spray drying is to be matched the solid phase using water
The slurries for being 10wt%~20wt% at concentration, and it is dry at≤100 DEG C.
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| CN105110382A (en) * | 2015-09-22 | 2015-12-02 | 升华集团德清华源颜料有限公司 | Method for preparing high-purity gamma-Fe2O3 iron oxide red pigment |
| CN105800762A (en) * | 2014-12-30 | 2016-07-27 | 北京三聚环保新材料股份有限公司 | Preparation method for amorphous FeOOH water-purifying agent |
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| CN102153146A (en) * | 2011-04-18 | 2011-08-17 | 中国科学院化学研究所 | Method for controllably preparing hydroxyl oxidize iron, iron sesquioxide and ferroferric oxide |
| CN105800762A (en) * | 2014-12-30 | 2016-07-27 | 北京三聚环保新材料股份有限公司 | Preparation method for amorphous FeOOH water-purifying agent |
| CN105110382A (en) * | 2015-09-22 | 2015-12-02 | 升华集团德清华源颜料有限公司 | Method for preparing high-purity gamma-Fe2O3 iron oxide red pigment |
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