CN109759018A - The preparation method and application of support type Manganese Ferrite adsorbent - Google Patents
The preparation method and application of support type Manganese Ferrite adsorbent Download PDFInfo
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Abstract
The present invention relates to environment protection fields, disclose a kind of preparation method and application of support type Manganese Ferrite adsorbent.The preparation method of support type Manganese Ferrite adsorbent includes: that (1) mixes vinasse with containing manganous salt and trivalent iron salt mixed liquor, mixed condition makes manganous salt and trivalent iron salt form Manganese Ferrite, and be carried on the vinasse, obtain support type Manganese Ferrite adsorbent precursors；(2) after the support type Manganese Ferrite adsorbent precursors drying and roasting, support type Manganese Ferrite adsorbent is obtained.The adsorbent has the advantages that excellent in magnetic characteristics, large specific surface area, surface-active site is high, chemical stability is good, while big to the adsorption efficiency of atoxylic acid height, adsorption capacity.
Description
Technical field
The present invention relates to environment protection fields, and in particular to a kind of preparation method and application of support type Manganese Ferrite adsorbent.
Background technique
For a long time, the arsenic in water body is always focus concerned by people to the harm of human health.Studies have shown that when long
Between drink the generation that the water containing low arsenic concentration also results in many diseases, therefore the minimizing technology of arsenic is always environmental area in water
The heat subject of research.Currently, the method for removal Pollutants in Wastewater mainly has: chemical precipitation or flocculence, membrane technology, electrolysis
Reduction, catalytic degradation, ion exchange and absorption method, wherein absorption method is because of its easy to operate, the wide variety of adsorbent, operation week
The advantages such as the phase is short, treatment effeciency is high and be widely used.
In numerous arsenicals, atoxylic acid is a kind of novel organoarsenium compound, is widely used in moving
The additive of object feed.However in recent years the study found that organoarsenium compound only has minimum a part could in animal body
It is metabolized or absorbs, rest part can be drained intactly in the form of excrement and urine, and wherein arsenic content is more than 40mg/
Kg, these water-soluble atoxylic acid are degraded to high poison by biology and abiotic approach in 30 days after excrement is drained
Property inorganic arsenic, causes soil and groundwater arsenic pollution serious, influences human health.Therefore, the p-aminophenyl in aqueous solution is removed
Arsenic acid also becomes the hot spot studied both at home and abroad.
Summary of the invention
The purpose of the invention is to overcome atoxylic acid in animal feed of the existing technology to cause water body dirty
The problem of dye, a kind of support type Manganese Ferrite adsorbent and preparation method thereof is provided, which has excellent in magnetic characteristics, specific surface
The advantage that product is big, surface-active site is high, chemical stability is good, while, absorption high to the adsorption efficiency of atoxylic acid is held
Amount is big.
To achieve the goals above, first aspect present invention provides a kind of preparation method of support type Manganese Ferrite adsorbent,
This method comprises:
(1) vinasse are mixed in containing manganous salt and trivalent iron salt mixed liquor, mixed condition makes divalent
Manganese salt and trivalent iron salt form Manganese Ferrite, and are carried on the vinasse, obtain support type Manganese Ferrite adsorbent precursors；
(2) after the support type Manganese Ferrite adsorbent precursors drying and roasting, support type Manganese Ferrite adsorbent is obtained.
Preferably, the condition of mixing described in step (1) include: pH be 9-11, temperature is 50-70 DEG C, time 3-5h.
Preferably, the trivalent iron salt based on 100 parts by weight in step (1), the dosage of the vinasse are 30-90 parts by weight,
The dosage of the manganous salt is 15-70 parts by weight.
Preferably, manganous salt described in step (1) is selected from manganese sulfate and/or manganese chloride, and the trivalent iron salt is selected from chlorine
Change at least one of iron, ferric sulfate and ferric nitrate.
It preferably, further include that the support type Manganese Ferrite adsorbent precursors are washed before the drying in step (2)
It washs.
Preferably, temperature dry described in step (2) be 90-110 DEG C, time 20-30h, the condition of the roasting
Include: in an inert atmosphere, temperature be 600-800 DEG C, time 0.5-2h.
Preferably, this method further includes being ground, being washed to the support type Manganese Ferrite adsorbent, dried, and is obtained most
Finished product.
Preferably, it is described grinding include the support type Manganese Ferrite adsorbent is ground to granularity be 100 mesh more than, it is described
The condition of washing includes using milli-Q water to the pH of cleaning solution for 6.5-7.0, and the temperature of the drying is 90-110 DEG C.
Second aspect of the present invention provides the support type Manganese Ferrite adsorbent prepared by the above method.
Third aspect present invention provides the support type Manganese Ferrite adsorbent prepared by the above method in removing p-aminophenyl arsine
Application in acid.
Through the above technical solutions, the invention has the following advantages that
1, support type Manganese Ferrite adsorbent of the invention utilizes manganous salt and ferric iron using vinasse as adsorbing agent carrier
Salt synthesis Manganese Ferrite is simultaneously carried on carrier, forms support type Manganese Ferrite adsorbent precursors, so that vinasse conversion is made a living by roasting
Object charcoal makes adsorbent have loose porous structure together so that charcoal and Manganese Ferrite preferably load；
2, support type Manganese Ferrite adsorbent of the invention has excellent magnetic characteristic, therefore can be by outer after the completion of absorption
Portion's magnetic fields realize the quick separating with liquid phase, avoid centrifugation or are separated by filtration bring inconvenience, facilitate recycling, drop
Low operation difficulty and cost, improve adsorption efficiency；
3, support type Manganese Ferrite adsorbent of the invention has more loose porous structure, apparent distribution of particles, height
Specific surface area has certain water solubility and dispersibility, provides more active site, has to atoxylic acid good
Absorption property；
4, support type Manganese Ferrite adsorbent preparation process of the invention is simple, low in cost, is suitable for large-scale production and answers
With；
5, support type Manganese Ferrite adsorbent of the invention is adsorbable and removes the atoxylic acid in water body, and adsorbs effect
Rate is high, and condition is easy to control, and chemical property is stablized, and can be widely used in the water body containing atoxylic acid.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of support type Manganese Ferrite adsorbent of the invention；
Fig. 2 is the transmission electron microscope picture of support type Manganese Ferrite adsorbent of the invention；
Fig. 3 is the pass that support type Manganese Ferrite adsorbent of the invention changes the adsorption efficiency of atoxylic acid with pH value
It is schematic diagram；
Fig. 4 is the pass that support type Manganese Ferrite adsorbent of the invention varies with temperature the adsorption efficiency of atoxylic acid
It is schematic diagram；
Fig. 5 is that support type Manganese Ferrite adsorbent of the invention changes the adsorption efficiency of atoxylic acid with adsorption time
Relation schematic diagram；
Fig. 6 be support type Manganese Ferrite adsorbent of the invention to the adsorption efficiency of atoxylic acid with atoxylic acid
The relation schematic diagram of initial concentration variation；
Fig. 7 is that support type Manganese Ferrite adsorbent of the invention becomes the adsorption efficiency of atoxylic acid with adsorbent amount
The relation schematic diagram of change.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention a kind of preparation method of support type Manganese Ferrite adsorbent is provided this method comprises:
(1) vinasse are mixed in containing manganous salt and trivalent iron salt mixed liquor, mixed condition makes divalent
Manganese salt and trivalent iron salt form Manganese Ferrite, and are carried on the vinasse carrier, obtain support type Manganese Ferrite adsorbent precursors；
(2) after the support type Manganese Ferrite adsorbent precursors drying and roasting, support type Manganese Ferrite adsorbent is obtained.
Preferably, the condition of mixing described in step (1) include: pH be 9-11, temperature is 50-70 DEG C, time 3-5h.
In the present invention, vinasse refer to remaining residue after the wine brewing such as rice, wheat, jowar.In order to be more conducive to described
The mixed process of absorption on vinasse carrier, vinasse and manganous salt and trivalent iron salt is preferred are as follows: vinasse mixed with ultrapure water,
Under the conditions of 22-28 DEG C, 20-35min is stirred, manganous salt and trivalent iron salt are then added to the complete spent wash of mixing
In, strong base solution is added after the solid is completely dissolved and adjusts pH value to 9-11, obtained mixture is put into thermostatic drying chamber
In reacted, wherein the strong base solution is preferably the sodium hydroxide solution of 5mol/L, be more advantageous to the formation of Manganese Ferrite with
Load.
Preferably, the trivalent iron salt based on 100 parts by weight in step (1), the dosage of the vinasse are 30-90 parts by weight,
It is specifically as follows 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, and
Any two in these point values constitute in the range of arbitrary value, the dosage of the manganous salt is 15-70 parts by weight, tool
Body can for 15 parts by weight, 25 parts by weight, 35 parts by weight, 45 parts by weight, 55 parts by weight, 65 parts by weight, 70 parts by weight and this
Arbitrary value in the range of any two in point values are constituted a bit.
Preferably, manganous salt described in step (1) is selected from manganese sulfate and/or manganese chloride, and the trivalent iron salt is selected from chlorine
Change at least one of iron, ferric sulfate and ferric nitrate.
It preferably, further include that the support type Manganese Ferrite adsorbent precursors are washed before the drying in step (2)
It washs, washing preferably filter after repeatedly washing using ultrapure water.
Preferably, temperature dry described in step (2) is 90-110 DEG C, be specifically as follows 90 DEG C, 95 DEG C, 100 DEG C,
Any two in 105 DEG C, 110 DEG C and these point values constitute in the range of arbitrary value, time 20-30h, specifically
Can any two for 20h, 22h, for 24 hours, in 26h, 28h, 30h and these point values constitute in the range of arbitrary value.
The condition of the roasting include: in an inert atmosphere, temperature be 600-800 DEG C, be specifically as follows 600 DEG C, 650 DEG C, 700
DEG C, 750 DEG C, any two in 800 DEG C and these point values constitute in the range of arbitrary value, calcining time 0.5-
2h, the arbitrary value being specifically as follows in the range of any two in 0.5h, 1h, 1.5h, 2h and these point values are constituted.
Wherein, the inert gas is preferably nitrogen.Material is preferably placed in quartz boat by roasting process, is put into heating rate 5
DEG C/tube furnace of min in calcined.
In the present invention, vinasse are carried out being mixed to form support type ferrous acid in containing manganous salt and trivalent iron salt mixed liquor
Manganese adsorbent precursors, then after drying and roasting, obtain support type Manganese Ferrite adsorbent.But the present inventor is grinding
It finds during studying carefully, after to the support type Manganese Ferrite adsorbent by further grinding, washing, is dry, can be made
More excellent performance of adsorbent final products.
The grinding, washing, drying process of the support type Manganese Ferrite adsorbent are not particularly limited in the present invention,
Such as can preferably, the grinding includes that the support type Manganese Ferrite adsorbent is ground to granularity using agate mortar to be
More than 100 mesh, the condition of the washing includes using milli-Q water to the pH of cleaning solution for 6.5-7.0, the temperature of the drying
Degree is 90-110 DEG C.
Second aspect, the present invention provides the support type Manganese Ferrite adsorbents prepared by the above method.
The third aspect, the present invention provides the support type Manganese Ferrite adsorbents prepared by the above method in removing p-aminophenyl
Application in arsenic acid.
The present invention will be described in detail by way of examples below.In following embodiment, electron microscope scanning is used
Scanning electron microscope, model QUANTA250FEG；Transmission electron microscope analysis uses transmission electron microscope, model Tecnal
G220；The concentration mensuration of atoxylic acid solution uses ultraviolet-uisible spectrophotometer, model UV1900；Vinasse come from wine
Gui Jiu limited liability company；Atoxylic acid is purchased from Ti Xiai chemical conversion industry Development Co., Ltd, specification GR；Other chemistry
Product are commercially available product.
Embodiment 1
(1) 5g vinasse are weighed to mix with 100mL ultrapure water, 30min is stirred under the conditions of 25 DEG C, makes vinasse substantially uniformity
It is dispersed in water, then by 5.5g MnSO4·4H2O and 8g Fe2(SO4)3It is added in spent wash, after the solid is completely dissolved
The pH value of mixed liquor is adjusted to 10 with the NaOH solution of 5mol/L, mixed liquor is put into 60 DEG C of drying boxes and reacts 4h；
(2) it by the sediment generated in mixed liquor (support type Manganese Ferrite adsorbent precursors) after being separated in mixed liquor, uses
Ultrapure water is cleaned multiple times, is filtered, and is dried at 100 DEG C for 24 hours, in N2It under environment, puts the precipitate in quartz boat, is put into
With 700 DEG C of calcining 1h in the tube furnace of 5 DEG C/min of heating rate, it is fully crystallized metal；
(3) in N2It after being cooled to room temperature step (2) products therefrom under environment, is ground using agate mortar, crosses 100 mesh
Sieve is repeatedly washed until the pH of cleaning solution reaches 6.5 with ultrapure water, product is dried at 100 DEG C, obtains support type Manganese Ferrite
Adsorbent.
Electron microscope observation is scanned to support type Manganese Ferrite adsorbent made from embodiment 1, as shown in Figure 1, iron
Together with manganese oxysome is preferably loaded with charcoal, charcoal loads Manganese Ferrite and has more loose porous structure, it will be apparent that
Distribution of particles has good absorption property.Transmission electron microscope point is carried out to support type Manganese Ferrite adsorbent made from embodiment 1
Analysis has certain water solubility and dispersion as shown in Fig. 2, the material dispersion effect of charcoal obtained load ferrimanganic oxysome is preferable
Property, more active site, this structure and its excellent magnetic characteristic are provided, its adsorption effect is advantageously implemented.
Embodiment 2
(1) 5g vinasse are weighed to mix with 100mL ultrapure water, 30min is stirred under the conditions of 25 DEG C, makes vinasse substantially uniformity
It is dispersed in water, then by 2.58g MnSO4·H2O and 14.8g FeCl3·6H2O is added in spent wash, to solid whole
The pH value of mixed liquor is adjusted to 9 with the NaOH solution of 5mol/L after dissolution, mixed liquor is put into 50 DEG C of drying boxes and reacts 5h；
(2) it by the sediment generated in mixed liquor (support type Manganese Ferrite adsorbent precursors) after being separated in mixed liquor, uses
Ultrapure water is cleaned multiple times, is filtered, the dry 30h at 90 DEG C, in N2It under environment, puts the precipitate in quartz boat, is put into
With 600 DEG C of calcining 2h in the tube furnace of 5 DEG C/min of heating rate, it is fully crystallized metal；
(3) in N2It after being cooled to room temperature step (2) products therefrom under environment, is ground using agate mortar, crosses 100 mesh
Sieve is repeatedly washed until the pH of cleaning solution reaches 6.5 with ultrapure water, product is dried at 90 DEG C, obtains support type Manganese Ferrite
Adsorbent.
Embodiment 3
(1) 8.7g vinasse are weighed to mix with 100mL ultrapure water, 30min is stirred under the conditions of 25 DEG C, makes vinasse substantially uniformity
Be dispersed in water, then by 4.46gMnCl2With 9.67g Fe (NO3)3It is added in spent wash, uses after the solid is completely dissolved
The NaOH solution of 5mol/L adjusts the pH value of mixed liquor to 11, and mixed liquor is put into 70 DEG C of drying boxes and reacts 3h；
(2) it by the sediment generated in mixed liquor (support type Manganese Ferrite adsorbent precursors) after being separated in mixed liquor, uses
Ultrapure water is cleaned multiple times, is filtered, the dry 20h at 110 DEG C, in N2It under environment, puts the precipitate in quartz boat, is put into
With 800 DEG C of calcining 0.5h in the tube furnace of 5 DEG C/min of heating rate, it is fully crystallized metal；
(3) in N2It after being cooled to room temperature step (2) products therefrom under environment, is ground using agate mortar, crosses 100 mesh
Sieve is repeatedly washed until the pH of cleaning solution reaches 7.0 with ultrapure water, product is dried at 110 DEG C, obtains support type Manganese Ferrite
Adsorbent.
Embodiment 4
(1) 10g vinasse are weighed to mix with 100mL ultrapure water, 30min is stirred under the conditions of 25 DEG C, makes vinasse substantially uniformity
Be dispersed in water, then by 2.5g MnCl2、3.38gMnSO4·4H2O and 12.9g FeCl3It is added in spent wash, to solid
Body is adjusted the pH value of mixed liquor to 10.5 with the NaOH solution of 5mol/L after all dissolving, and mixed liquor is put into 55 DEG C of drying boxes
Middle reaction 4h；
(2) it by the sediment generated in mixed liquor (support type Manganese Ferrite adsorbent precursors) after being separated in mixed liquor, uses
Ultrapure water is cleaned multiple times, is filtered, the dry 20h at 80 DEG C, in N2It under environment, puts the precipitate in quartz boat, is put into
With 400 DEG C of calcining 2h in the tube furnace of 5 DEG C/min of heating rate, it is fully crystallized metal；
(3) in N2It after being cooled to room temperature step (2) products therefrom under environment, is ground using agate mortar, crosses 100 mesh
Sieve is repeatedly washed until the pH of cleaning solution reaches 6.5 with ultrapure water, product is dried at 80 DEG C, obtains support type Manganese Ferrite
Adsorbent.
Embodiment 5
(1) 10g vinasse are weighed to mix with 100mL ultrapure water, 30min is stirred under the conditions of 25 DEG C, makes vinasse substantially uniformity
Be dispersed in water, then by 5g MnCl2With 8g Fe2(SO4)3、10.8g FeCl3·6H2O is added in spent wash, to solid
Body is adjusted the pH value of mixed liquor to 9.5 with the NaOH solution of 5mol/L after all dissolving, and mixed liquor is put into 40 DEG C of drying boxes
Middle reaction 3h；
(2) it by the sediment generated in mixed liquor (support type Manganese Ferrite adsorbent precursors) after being separated in mixed liquor, uses
Ultrapure water is cleaned multiple times, is filtered, the dry 20h at 90 DEG C, in N2It under environment, puts the precipitate in quartz boat, is put into
With 600 DEG C of calcining 2h in the tube furnace of 5 DEG C/min of heating rate, it is fully crystallized metal；
(3) in N2After being cooled to room temperature step (2) products therefrom under environment, repeatedly washed with ultrapure water until cleaning solution
PH reach 5.5, product is dried at 90 DEG C, obtains support type Manganese Ferrite adsorbent.
Comparative example 1
The preparation of support type Manganese Ferrite adsorbent is carried out in the way of embodiment 1, unlike, it is replaced using ferrous chloride
Change ferric trichloride.
Comparative example 2
The preparation of support type Manganese Ferrite adsorbent is carried out in the way of embodiment 1, unlike, it is substituted using active carbon
Vinasse.
Test case 1-7
Atoxylic acid solution concentration of standard solution used in test is 1000ppm (1000mg/L), other concentration
Thus titer dilutes to obtain atoxylic acid solution, and 4- (dimethylamino) benzaldehyde solution is prepared by 1:9 hydrochloric acid solution,
Test carries out in the polyethylene bottle of 100mL.
Prepare the atoxylic acid solution that 7 groups of 50mL concentration are 20mg/L.50mg reality is separately added into above-mentioned solution
The support type Manganese Ferrite adsorbent for applying example and comparative example preparation, is adsorbed under the conditions of temperature is 25 DEG C, pH=2, sufficiently anti-
Should after sample, by sample solution by the filtering of 0.45 μm of water system miillpore filter after, it is molten that 1mL 4- (dimethylamino) benzaldehyde is added
Liquid calculates adsorption capacity and absorption with the concentration of the atoxylic acid solution after ultraviolet-uisible spectrophotometer measurement absorption
Rate, the results are shown in Table 1.
It can be seen that the support type Manganese Ferrite adsorbent compared to comparative example 1-2 preparation by the result of table 1, using this
The support type Manganese Ferrite adsorbent of invention preparation method has an adsorption effect of better atoxylic acid, and adsorption capacity compared with
Height can effectively remove atoxylic acid in a short time.
Table 1
| Number | Adsorption capacity (mg/g) | Adsorption rate (%) |
| Embodiment 1 | 18.00 | 89.33 |
| Embodiment 2 | 17.12 | 84.00 |
| Embodiment 3 | 16.66 | 82.27 |
| Embodiment 4 | 16.00 | 80.08 |
| Embodiment 5 | 15.07 | 75.43 |
| Comparative example 1 | 11.36 | 55.74 |
| Comparative example 2 | 11.16 | 55.51 |
Test case 8
Be respectively adopted the solution of different pH value, different sorption reaction times, different initial concentrations atoxylic acid,
Different quantity of sorbent and different temperatures, support type Manganese Ferrite adsorbent prepared by testing example 1 is in adsorption aqueous solution
The ability of atoxylic acid.Atoxylic acid solution concentration of standard solution used in test is 1000ppm (i.e. 1000mg/
L), thus titer dilutes to obtain the atoxylic acid solution of other concentration, and 4- (dimethylamino) benzaldehyde solution is by 1:9
Hydrochloric acid solution is prepared, and test carries out in the polyethylene bottle of 100mL.
1, influence of the pH value to support type Manganese Ferrite adsorbent adsorption capacity
Prepare the atoxylic acid solution that 10 groups of 50mL concentration are 20mg/L, uses 0.1mol/L HCl and 0.1mol/L
The initial pH that NaOH adjusts solution is respectively 2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.0,11.0, to above-mentioned molten
The support type Manganese Ferrite adsorbent of the preparation of 50mg embodiment 1 is separately added into liquid, after sufficiently reaction is carried out under the conditions of 25 DEG C or so
By sample solution by 0.45 μm of water system miillpore filter filtering 1mL 4- (dimethylamino) benzaldehyde solution is added, with purple in sampling
Atoxylic acid solution concentration after outer visible spectrophotometer measurement absorption.Experimental result as shown in figure 3, when pH=2.0,
The absorption of atoxylic acid is the most significant, and the support type Manganese Ferrite adsorbent that the raising of pH inhibits embodiment 1 to prepare is to right
The absorption of atoxylate, at pH=2.0, adsorbent is 18mg/g, pH value to the maximum adsorption capacity of atoxylic acid
When being increased to 3.0, adsorption capacity drops sharply to 6.67mg/g, and pH value range than more gentle between 5.0-11.0, hold by absorption
Amount variation is little.
2, influence of the temperature to support type Manganese Ferrite adsorbent adsorption capacity
Prepare the atoxylic acid solution that 3 groups of 50mL concentration are 20mg/L.50mg reality is separately added into above-mentioned solution
The support type Manganese Ferrite adsorbent for applying the preparation of example 1 is respectively placed under the conditions of 25 DEG C, 35 DEG C, 45 DEG C and pH=2.0 and is adsorbed,
It is sufficiently sampled after reaction, after sample solution is filtered by 0.45 μm of water system miillpore filter, 1mL 4- (dimethylamino) benzene is added
Formalin, with the concentration of the atoxylic acid solution after ultraviolet-uisible spectrophotometer measurement absorption.Experimental result such as Fig. 4
Shown, between 25 DEG C -35 DEG C, which has very big promotion to the adsorption rate of atoxylic acid, but at 35 DEG C -45 DEG C
When, as the temperature rises, adsorption effect reduces instead, it will thus be seen that high temperature is not suitable for adsorption reaction.Test measures most
Good laboratory scale adsorption reaction temperature is 35 DEG C, for the considerations of increasing difficulty to temperature in practical removal process, be may be selected
25 DEG C or adsorption test or adsorption applications are carried out under room temperature.
3, influence of the adsorption time to support type Manganese Ferrite adsorbent adsorption capacity
Prepare the atoxylic acid solution that 1 part of 50mL concentration is 20mg/L, 50mg embodiment 1 is added in Xiang Shangshu solution
The support type Manganese Ferrite adsorbent of preparation is adsorbed under the conditions of temperature is 25 DEG C, pH=2, primary every 40min sampling,
After sample solution is filtered by 0.45 μm of water system miillpore filter, 1mL 4- (dimethylamino) benzaldehyde solution is added, use is ultraviolet
Atoxylic acid solution concentration after visible spectrophotometer measurement absorption.Experimental result as shown in figure 5, in preceding 360min,
The removal rate of atoxylic acid is very fast, and support type Manganese Ferrite adsorbent is completely dissolved in atoxylic acid foul solution at this time
In, be conducive to quick adsorption, with the growth of time, the removal rate of atoxylic acid is gradually gentle, reaches suction in 1440min
Attached balance, removal rate have reached 86.43%.
4, influence of the initial concentration of atoxylic acid to support type Manganese Ferrite adsorbent adsorption capacity
Prepare the atoxylic acid solution of 9 groups of 50mL, initial concentration be respectively 5mg/L, 10mg/L, 25mg/L,
30mg/L, 50mg/L, 75mg/L, 100mg/L, 200mg/L, 300mg/L are separately added into 50mg embodiment 1 in Xiang Shangshu solution
The support type Manganese Ferrite adsorbent of preparation is adsorbed under the conditions of temperature is 25 DEG C, pH=2, is sufficiently sampled after reaction, by sample
After product solution is by 0.45 μm of water system miillpore filter filtering, 1mL 4- (dimethylamino) benzaldehyde solution is added, uses UV, visible light
The concentration of atoxylic acid solution after spectrophotometric determination absorption.Experimental result is as shown in fig. 6, with initial concentration
It increases, removal rate has substantial degradation, and the initial concentration of atoxylic acid has the suction-operated of the adsorbent larger
Influence.
5, influence of the adsorbent amount to support type Manganese Ferrite adsorbent adsorption capacity
Prepare the atoxylic acid solution that 6 groups of 50mL concentration are 20mg/L, is separately added into the support type of the preparation of embodiment 1
Manganese Ferrite adsorbent 10mg, 20mg, 30mg, 50mg, 70mg, 90mg are adsorbed under the conditions of temperature is 25 DEG C, pH=2, are filled
It is sampled after dividing reaction, after sample solution is filtered by 0.45 μm of water system miillpore filter, 1mL 4- (dimethylamino) benzene first is added
Aldehyde solution, with the concentration of the atoxylic acid solution after ultraviolet-uisible spectrophotometer measurement absorption.Experimental result such as Fig. 7 institute
Show, with increasing for support type Manganese Ferrite adsorbent dosage, the removal rate of atoxylic acid is gradually increased, and residue is to amino
Phenylarsine acid concentration gradually decreases, and when adsorbent dosage is 50mg, the removal rate of atoxylic acid reaches 84%, later with
Dosage increases, and the ascensional range of removal rate tends towards stability.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of support type Manganese Ferrite adsorbent, which is characterized in that this method comprises:
(1) vinasse are mixed with containing manganous salt and trivalent iron salt mixed liquor, mixed condition make manganous salt and
Trivalent iron salt forms Manganese Ferrite, and is carried on the vinasse, obtains support type Manganese Ferrite adsorbent precursors；
(2) after the support type Manganese Ferrite adsorbent precursors drying and roasting, support type Manganese Ferrite adsorbent is obtained.
2. the method according to claim 1, wherein it is 9- that the condition of mixing described in step (1), which includes: pH,
11, temperature be 50-70 DEG C, time 3-5h.
3. the method according to claim 1, wherein the trivalent iron salt based on 100 parts by weight in step (1), institute
The dosage for stating vinasse is 30-90 parts by weight, and the dosage of the manganous salt is 15-70 parts by weight.
4. the method according to claim 1, wherein manganous salt described in step (1) be selected from manganese sulfate and/or
Manganese chloride, the trivalent iron salt are selected from least one of iron chloride, ferric sulfate and ferric nitrate.
5. the method according to claim 1, wherein further including before the drying in step (2) to described negative
Load type Manganese Ferrite adsorbent precursors are washed.
6. the method according to claim 1, wherein temperature dry described in step (2) be 90-110 DEG C, when
Between be 20-30h, the condition of the roasting include: in an inert atmosphere, temperature be 600-800 DEG C, time 0.5-2h.
7. method as claimed in any of claims 1 to 6, which is characterized in that this method further includes to the load
Type Manganese Ferrite adsorbent is ground, is washed, is dried, and final products are obtained.
8. the method according to the description of claim 7 is characterized in that the grinding includes by the support type Manganese Ferrite adsorbent
Being ground to granularity is 100 mesh or more, and the condition of the washing includes using milli-Q water to the pH of cleaning solution for 6.5-7.0,
The temperature of the drying is 90-110 DEG C.
9. the support type Manganese Ferrite adsorbent of the preparation of method described in any one of claim 1-8.
10. application of the support type Manganese Ferrite adsorbent as claimed in claim 9 in removing atoxylic acid.
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| CN201910218395.5A CN109759018A (en) | 2019-03-21 | 2019-03-21 | The preparation method and application of support type Manganese Ferrite adsorbent |
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