CN101970099A - Selective adsorbent material, and method for production thereof - Google Patents
Selective adsorbent material, and method for production thereof Download PDFInfo
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- CN101970099A CN101970099A CN2009801036830A CN200980103683A CN101970099A CN 101970099 A CN101970099 A CN 101970099A CN 2009801036830 A CN2009801036830 A CN 2009801036830A CN 200980103683 A CN200980103683 A CN 200980103683A CN 101970099 A CN101970099 A CN 101970099A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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Abstract
Disclosed is a method for efficiently removing a nitrate ion, an arsenic ion and a phosphate ion simultaneously with a single adsorbent material with less interference of coexisting anions or the like. Specifically disclosed is an adsorbent material comprising hydrotalcite microparticles each represented by formula (1) [wherein x represents a positive number of more than 0.15 and less than 0.34; An- represents a n-valent anion excluding Cl-; y represents a positive number; and m represents a positive number of more than 0.1 and less than 0.7] and a polyvalent metal compound which is amorphous as observed by X ray diffraction and is arranged on the surfaces of the hydrotalcite microparticles. Also specifically disclosed is a method for producing the adsorbent material. Mg1-xAlx(OH)2(Cl)x-ny (An-)y mH2O (1).
Description
Technical field
The present invention relates to can be from the aqueous solution simultaneously and the selective absorption adsorbent and the manufacture method thereof of removing nitrate ion, phosphorus and arsenic.
Background technology
Arsenic not only has acute toxicity, also has carcinogenicity and chronic toxicity, so in environment Basic Law " the water quality benchmark of public waters ", perhaps in " province about the water quality benchmark based on the water channel method makes ", set up the following benchmark of 0.01mg/L.Thereby, in order to utilize underground water, river water, lake water etc., must remove the arsenic in these processing water as drinking water.Compare with plant drainage source, arsenic more is to derive from the earth's crust, has the problem of polluting well water etc. in the underground water route that is dissolved in.
In river water or underground water, arsenic is that the form with the arsenic acid of the arsenious acid of 3 valencys or 5 valencys exists on almost, and particularly in reducing atmospheres such as underground water, the arsenious acid of 3 valencys is overriding.At present, the arsenious acid of 3 valencys adopts adsorption treatment to be difficult to remove, and most cases is to carry out pre-treatment earlier, and the arsenic acid that is oxidized to 5 valencys is handled afterwards again.
The method of typically removing of arsenic is known flocculent precipitation and absorption method.Flocculent precipitation is a kind of the interpolation in handling water after the inorganic flocculating agents such as aluminium salt or molysite, when adjustment pH value makes metal hydroxides aggregate precipitation, thereby makes arsenic enter this aggregate method of co-precipitation separation with it.But, flocculent precipitation is according to arsenic concentration a large amount of flocculant of needs in it is handled, and the dreg containing arsenic of generation is bulky amorphous state, so sedimentation needs big equipment and a large amount of time, in addition, a large amount of mud that generate and processing complexity, the trouble of filtering material.In addition, adopt the situation of flocculent precipitation, must use oxidant to remove processing again after the arsenious acid of 3 valencys being oxidized to the arsenic acid of 5 valencys in advance.
Absorption method is a kind ofly the processing water that contains arsenic to be contacted with adsorbent make it to adsorb the method for removing, and adsorbent can use active carbon, activated alumina, zeolite, metatitanic acid, hydrous zirconium thing etc.
Use the method for known arsenic adsorbent such as cerium, iron powder and activated alumina to compare, can obtain the excellent efficient of removing, but, can't obtain the practical arsenic that to be satisfied with of going up and remove effect insufficient aspect the selectivity of arsenic with flocculent precipitation.In addition, since known arsenic adsorbent such as cerium, iron powder and activated alumina etc. Electricity point near neutrality, so thereby existing the pH that handles water to surpass 7～8 o'clock surface charges changes and bear the shortcoming that loses adsorption capacity.
Zirconium be adsorbent known zirconium, zirconia, zirconium carbonate, basic zirconium phosphate, oxidizing aqueous zirconium etc. are arranged, these zirconium compounds are by granulation or be supported on the enterprising enforcement of carrier with (patent documentation 1 and non-patent literature 3).Carrier can be enumerated nonwoven (patent documentation 2), magnalium composite oxides (patent documentation 3), goethite (patent documentation 4) and cation exchange base mating type silica gel (non-patent literature 3), the spherical resin pearl (non-patent literature 4) etc. that reactive monomer with phosphate obtains by glycerol polymerization.
Having used arsenous anion ion or arsenate ion adsorbent in the aqueous solution of hydrotalcite or pyrolite disclosed by non-patent literature 1, patent documentation 5 and patent documentation 9, is known adsorbent.A part of having put down in writing the carbanion of hydrotalcite in non-patent literature 1, patent documentation 6 and the patent documentation 7 is chlorinated that the thing ion replaces and the use in the removing of arsenic of the compound that forms.But, when not addressing competing ions in the above-mentioned document and existing to the adsorptive selectivity of arsenic.
Disclose in the patent documentation 8 and not polluted by carbonic acid that Carbon Dioxide in Air causes or can keep the hydrotalcite of handling anion adsorption capacity in the water with the influence of handling carbanion competition in the water.
Put down in writing among 0006 section of patent documentation 8 and the embodiment 1: rapid mixing stirs the mixed acid solution and the sodium hydrate aqueous solution of magnesium nitrate and aluminum nitrate, and adjusts Na
+/ Mg
2+Mol than the scope that is 2.5～3.0, make reaction system maintain below the pH8 all the time, the dope filtration that obtains, washing, drying are even obtain having the hydrotalcite that also can bring into play desired anion exchange capacity under the environment that existence such as carbon dioxide or carbanion, sulfate ion, nitrate ion, chloride ion are arranged of high anion exchange capacity thus.But adsorptivity when all not putting down in writing arsenic and nitric acid in non-patent literature 1, the patent documentation 6～8.
In recent years, the ammonia that contains in the fertilizer of crop land or the living drainage is oxidized and underground water pollution that nitric nitrogen that generate causes becomes problem.Under the situation of nitric nitrogen huge uptake, its part is by the micro-reduction in the digestive organs, form with nitrite nitrogen is absorbed in vivo, in blood and hemoglobin in conjunction with becoming ferrihemoglobin, cause methemoglobinemia, nitric nitrogen also generates carcinogenicity N one nitroso compound under one's belt.Therefore, in environment Basic Law " the water quality benchmark of public waters " or in " province about the water quality benchmark based on the water channel method makes ", set up the benchmark below the 10mg/L.Thereby, in order to utilize underground water, river water and lake water etc., must remove the nitrate ion in these processing water as drinking water.
Physico-chemical processes such as biological method that the employing microorganism is arranged that the technology of removing of nitrate ion is known and ion-exchange, electroosmose process, contrary impregnating method, absorption method.In the said method, so absorption method is a kind of method of removing of excellence because of its simplicity.Adsorbent is known charcoal that iron chloride handled and black andosol etc., wishes to develop the technology that the more cheap raw material of a kind of usefulness can effectively be removed nitrate ion.
The ability that 2 pairs of non-patent literatures are removed phosphoric acid, nitrate ion as shown in the formula the Mg-Fe-Al-Cl type hydrotalcite shown in (2) is put down in writing.
Mg
0.666Fe(III)
0.162Al
0.172(OH)
2(Cl)
0.140·(CO
3)
0.0121·0.328H
2O (2)
But when phosphoric acid and carbanion coexistence, the hydrotalcite of formula (2) is low to the selectivity of nitrate ion, so almost can not remove nitrate ion.
Disclosing a kind of nitrate ion adsorbent in the patent documentation 10, it is characterized in that, is active ingredient to be selected from least a in the crystallinity complex metal hydroxide shown in the following formula (3), its hydrothermal treatment consists thing and their the heat treated thing.
[Ni(II)
0.79Fe(III)
0.21(OH)
2][(Cl)
0.21·0.63H
2O] (3)
According to 0009 section record of patent documentation 10, also can use Co (II), Zn (II), Fe (II), Cu (II) to replace Ni, Fe (III) also can wait other 3 valency metals to replace with Al (III).In addition, according to 0010 section record, the ion exchangeable of consideration and nitrate ion, Cl
-Also can replace to HCO
3 -, OH
-, CO
3 2-Or NO
3 -But, in the patent documentation 10 adsorbent of while arsenic-adsorbing is not put down in writing.
The clear heir of very clear, the difficult to understand rib of people, Ji Gangminming, Mei Jin is known in [non-patent literature 1] " hydrotalcite application in water environment is saved from damage and purified " tortoise field; The Chemical Times 2005 No.1 are logical to calculate No. 200 p.10-16 (Kanto Kagaku K. K.'s distribution)
[non-patent literature 2] " Removal Characteristics of Phosphate and NitrateIons with an Mg-Fe-Al-Cl Form Hydrotalcite ", Tomiyuki Kuwabara, HideoKimura, Shunzi Sunayama, Ariumi Kawamoto, Hisamitsu Oshima andToshio Sato; Journal of Society of Inorganic Materials, Japan 14,17-25 (2007)
[non-patent literature 3] " adopt solid phase extraction to collect simultaneously at the scene simply to concentrate/quantitatively arsenic (III) and the arsenic (V) in the ambient water ", harvest in village difficult to understand, rattan smokes forever, clear family Thailand, Tian Meixiang, loose tail brother forever; BUNSEKI KAGAKU vol.52, No.12pp.1147-1152 (2003)
[non-patent literature 4] " Removal of As (III) and As (V) by a Porous SphericalResin Loaded with Monoclinic Hydrous Zirconium Oxide ", Toshishige M.Suzuki, John O.Bomani, Hideyuki Matsunaga and ToshiroYokoyama; Chemistry Letters vol.26 No.11p.1119-1120 (1997)
[patent documentation 1] spy opens flat 10-165948 communique
[patent documentation 2] spy opens the 2004-188307 communique
[patent documentation 3] spy opens the 2000-70927 communique
[patent documentation 4] spy opens the 2007-196170 communique
[patent documentation 5] spy opens the 2000-33387 communique
[patent documentation 6] spy opens the 2007-741 communique
[patent documentation 7] spy opens the 2000-233188 communique
[patent documentation 8] spy opens the 2006-334456 communique
[patent documentation 9] spy opens the 2001-233619 communique
[patent documentation 10] spy opens the 2004-130200 communique
Summary of the invention
As everyone knows, hydrotalcite (following abbreviate as sometimes " HT ") particulate is a kind of adsorbent that adsorbs inorganic anion and organic anion by ion-exchange reactions rapidly.
But in fact, the ion-exchange selectivity of common HT is big for multivalent anions, and it is little for 1 valency anion, more little for the little nitrate ion of charge density, with other anionic coexistence system in, its almost hopeless can absorption removing.
Thereby the object of the present invention is to provide a kind of is adsorbent to the big hydrotalcite of the adsorption capacity of nitrate ion and arsenic.In addition, the present invention also aims to provide a kind of adsorbent big to the selectivity of nitrate ion and arsenic.In addition, the present invention also aims to provide a kind of counter anion that less is subjected to disturb the adsorbent that effectively to remove nitrate ion and arsenic.In addition, the present invention also aims to provide a kind of and can adsorb the selected adsorbent of the safety of removing nitrate ion and arsenic simultaneously.
In addition, the present invention also aims to provide a kind of manufacture method of described adsorbent.
The inventor has found the adsorbent of excellent nitrate ion, thereby is conceived to constitute the kind of divalent metal ion, 3 valence metal ions and anion kind of hydrotalcite and the mol ratio of metal ion is studied.The result has obtained following opinion: in Mg-Al-Cl type hydrotalcite particulate, Al/ (Mg+Al) is when 0.16～0.20 scope, and the nitrate ion adsorptivity is the most excellent.That is, obtained Mg/Al as shown in figure 24 when 4～5.26 scope, the selection coefficient of nitrate ion surpasses 100, selects the experimental data of adsorptivity excellence.
And find, adopt the soluble-salt aqueous solution of polyvalent metal that this particle is handled, make the surface have polyvalent metal compounds, then not only keep excellent nitrate ion adsorptivity, also arsenic and phosphate anion are demonstrated excellent adsorptivity, thereby finished the present invention.
That is, the present invention relates to:
1. adsorbent, what comprise that the hydrotalcite particulate of following formula (1) expression and surface thereof exist confirms as amorphous polyvalent metal compounds according to X-ray diffraction,
Mg
1-xAl
x(OH)
2(Cl)
x-ny·(A
n-)
y·mH
2O (1)
In the formula, x is for satisfying the positive number of 0.15＜x＜0.34, A
N-Be Cl
-N valency anion in addition, y is a positive number, m is for satisfying the positive number of 0.1＜m＜0.7;
2. above-mentioned 1 described adsorbent, wherein, polyvalent metal compounds is oxide, hydroxide or their compound;
3. above-mentioned 1 described adsorbent, wherein, polyvalent metal compounds is for being selected from the compound of at least a kind of metal among Zr (IV), Fe (III), Ti (IV) and the Ce (IV);
4. above-mentioned 1 described adsorbent, wherein, the hydrotalcite particulate is the synthetic particulate that obtains of hydro-thermal under the temperature more than 100 ℃;
5. above-mentioned 1 described adsorbent, wherein, the particulate of hydrotalcite particulate for more than hydro-thermal Synthetic 2 under 150～180 ℃ the temperature hour, obtaining;
6. above-mentioned 1 described adsorbent, wherein, according to the oxide conversion of polyvalent metal, the amount of polyvalent metal compounds is 2～30 weight % with respect to the adsorbent total amount;
7. above-mentioned 1 described adsorbent, wherein, in formula (1), x satisfies 0.16≤x≤0.20;
8. above-mentioned 1 described adsorbent, wherein, in formula (1), (x-ny)/satisfied 0.6≤(the x-ny)/x of x≤1.0;
9. above-mentioned 1 described adsorbent wherein, has adsorptivity simultaneously to nitrate ion, phosphate anion and arsenic;
10. the manufacture method of adsorbent comprises: in temperature below 60 ℃, stir under, in the outstanding muddy water solution of the hydrotalcite particulate of following formula (1) expression, inject the soluble-salt of polyvalent metal, polyvalent metal compounds is separated out on the surface of hydrotalcite particulate,
Mg
1-xAl
x(OH)
2(Cl)
x-ny·(A
n-)
y·mH
2O (1)
In the formula, x is for satisfying the positive number of 0.15＜x＜0.34, A
N-Be Cl
-N valency anion in addition, y is a positive number, m is for satisfying the positive number of 0.1＜m＜0.7;
11. above-mentioned 10 described manufacture methods, wherein, the soluble-salt of polyvalent metal is for being selected from the chloride or the sulfate of at least a kind of metal among Fe (III), Zr (IV), Ti (IV), Ce (III) and the Ce (IV).
Description of drawings
Fig. 1 is the SEM photo of the adsorbent in the synthesis example 1 of embodiment.
Fig. 2 is the SEM photo of the adsorbent in the synthesis example 3 of embodiment.
Fig. 3 is the SEM photo of the adsorbent in the synthesis example 5 of embodiment.
Fig. 4 is the SEM photo of the adsorbent in the synthesis example 9 of embodiment.
Fig. 5 is the SEM photo of the adsorbent in the synthesis example 10 of embodiment.
Fig. 6 is the SEM photo of the adsorbent in the synthesis example 13 of embodiment.
Fig. 7 is the SEM photo of the adsorbent in the synthesis example 19 of embodiment.
Fig. 8 is the SEM photo of the adsorbent in the synthesis example 21 of embodiment.
Fig. 9 is the SEM photo of the adsorbent in the synthesis example 22 of embodiment.
Figure 10 is the SEM photo of the adsorbent in the synthesis example 25 of embodiment.
Figure 11 is the SEM photo of the adsorbent in the synthesis example 26 of embodiment.
Figure 12 is the SEM photo of the adsorbent in the synthesis example 27 of embodiment.
Figure 13 is the X-ray diffractogram of the adsorbent in the synthesis example 1 of embodiment.
Figure 14 is the X-ray diffractogram of the adsorbent in the synthesis example 5 of embodiment.
Figure 15 is the X-ray diffractogram of the adsorbent in the comparative example 1 of embodiment.
Figure 16 is the X-ray diffractogram of the adsorbent in the comparative example 2 of embodiment.
Figure 17 is the X-ray diffractogram of the adsorbent in the synthesis example 9 of embodiment.
Figure 18 is the X-ray diffractogram of the adsorbent in the synthesis example 13 of embodiment.
Figure 19 is the X-ray diffractogram of the adsorbent in the synthesis example 23 of embodiment.
Figure 20 is the X-ray diffractogram of the adsorbent in the synthesis example 25 of embodiment.
Figure 21 is a TEM photo of observing the platelike crystal end face of the adsorbent in the synthesis example 21 of embodiment.
Figure 22 is a TEM photo of observing the platelike crystal end face of the adsorbent in the synthesis example 27 of embodiment.
Figure 23 is the figure of adsorption rate of the adsorption experiment example 1 of expression embodiment.
Figure 24 is the figure that concerns between the selection coefficient of ratio of components Mg/Al and nitrate ion in the Mg-Al-Cl type hydrotalcite particulate in the adsorption experiment example 2 of expression embodiment.
The specific embodiment
＜adsorbent 〉
(hydrotalcite particulate)
The hydrotalcite particulate is the particulate of the hydrotalcite of following formula (1) expression.As the formula (1), the main composition element is magnesium and aluminium, and it is white and safe compound.
Mg
1-xAl
x(OH)
2(Cl)
x-ny·(A
n-)
y·mH
2O (1)
In the formula (1), x is for satisfying the positive number of 0.15＜x＜0.34.X only obtains the crystalline phase of HT substantially when satisfying the scope (i.e. 1.94＜Mg/Al＜5.67) of 0.15＜x＜0.34.
From 1 valency anion, particularly nitrate ion exchange selectivity this point, preferred x satisfies 0.16≤x≤0.20.When this scope, few as the solid solution capacity of the Al of center of positive charge, so Al is configured direct charge neutrality multivalent anions, thereby can not stablize multivalent anions each other across the interval of lattice paprmeter more than 2 times.Therefore, for 1 valency anion, be favourable, for the nitrate ion of the oxyacid that oxygen atom is arranged at grade, be favourable particularly, select adsorptivity to improve.The distribution coefficient KdNO that this changes with respect to Mg/Al from the expression nitrate ion
3Figure 24 of the measurement result of value is conspicuous.
A
N-Be Cl
-The anion of n valency in addition.A
N-Can enumerate the carbanion that comes from atmosphere that in the manufacturing of adsorbent, enters inevitably.Y is a positive number.Preferred 0＜the y of Y＜0.4x.Particularly, preferred y is 0～0.13.N is anionic valence mumber.N is preferably 1,2 or 3.
In the present invention, because HT has chloride ion as interlayer anion, so in the formula (1), x-ny=x (that is y=0) is desirable.It is more little that chloride ion mol counts x-ny, and adsorption capacity is more little.Preferred x-ny=x satisfies 0.6≤(x-ny)/x≤1.0.
In the formula (1), mH
2O represents intermediary water.M satisfies 0.1＜m＜0.7.That is, the HT that uses among the present invention is have intermediary water water type.The interlayer of decision HT every be the anion and the intermediary water of interlayer, for keep the interlayer of optimum nitrate ion by ion-exchange selectivity insertion every, this intermediary water also plays a role.
The product that the HT particulate that uses among the present invention also can directly use the coprecipitation reaction method to obtain, but preferred under the temperature more than 100 ℃ the synthetic product that obtains of hydro-thermal.The more preferably product that obtains more than the hydro-thermal Synthetic 2 hour under 150～180 ℃ the temperature.
Preferred each platelike crystal particle of HT particulate independently exists and the particulates of the whole openings of particle end face of ion gateway when carrying out anion exchange as interlayer.
(polyvalent metal compounds)
Adsorbent of the present invention has polyvalent metal compounds at above-mentioned HT microparticle surfaces.So-called polyvalent metal compounds specifically is meant Zr (IV), Fe (III), Ce (IV), TI (IV), V (V), Mn (II), Mn (III), Mn (IV), Mn (VI), Mn (VII), Cu (II), Co (II), Co (III), Mo (II), Mo (III), Mo (IV), Mo (V), Mo (VI), Ni (II), Ni compounds such as (III) among the present invention.
Polyvalent metal compounds be the hydrous oxide of polyvalent metal, promptly, oxide, hydroxide or their compound.Consider that from selecting adsorptivity and cost aspect polyvalent metal compounds is oxide, hydroxide or their compound of Zr (IV), Fe (III), Ce (IV) or Ti (IV).
The polyvalent metal compounds that the HT microparticle surfaces is separated out among the present invention is an amorphous state.So-called " amorphous state " is meant according to X-ray diffraction and confirms as amorphous state.
In the X-ray diffractogram of adsorbent of the present invention, do not observe the oxide crystallization of polyvalent metal or the peak of hydroxide crystallization, only observe the diffracted ray of HT, confirm as amorphous state so can confirm this polyvalent metal compounds according to X-ray diffraction.In addition, this fact, also is supported along with the increase of polyvalent metal compounds amount will be held the much bigger BET specific area compared with beginning material HT from described adsorbent.
It is generally acknowledged in the oxide crystallization of polyvalent metals such as zirconium, iron, cerium and titanium or hydroxide crystallization the anion adsorptivity is arranged, but because they have crystal structure, so the BET specific area is little, also few as the surface hydroxyl of adsorption site, thereby be inadequate as adsorbent.On the other hand, its BET specific area of adsorbent of the present invention is big, and is also many as the surface hydroxyl of adsorption site, so the adsorption capacity height.
Adsorbent of the present invention is to obtain by above-mentioned HT is handled with the aqueous solution of the soluble-salt of polyvalent metal.That is, polyvalent metal compounds is amorphous compound that the soluble-salt hydrolysis of polyvalent metal generates.
The polyvalent metal compounds that the HT microparticle surfaces is separated out is the amorphous state hydrous oxide that crystallization is stoped.Particularly, be that near the aluminium ion and the polyvalent metal compounds of acidic region (low reach 4) forms a spot of co-precipitation from precipitation pH, and it is low to generate pH, can infer that polyvalent metal compounds contains a spot of chloride ion, thus the amorphous state of remaining.And, be considered to also to have formed that 3 valency aluminium ion generation isomorphs on the part in 3 valencys of polyvalent metal compounds and 4 valence metal ion sites replace and the hydrous oxide that enters is inferred thus owing to these a plurality of reason crystallizations are stoped.
Convert with metal oxide, the weight of polyvalent metal compounds in the scope of 2～40 weight % the time, can obtain the good adsorption performance, more preferably the scope of 2～30 weight % with respect to the adsorbent gross weight.During less than 2 weight %, adsorption capacity is low, and when surpassing 40 weight %, HT can not keep its structure.
Selected adsorbent of the present invention is characterised in that, can adopt a kind of adsorbent selective absorption simultaneously nitrate ion, phosphonium ion and arsenic etc. human health to be harmful to or to cause the multiple solute composition of water environment eutrophication.
The manufacture method of＜adsorbent 〉
Adsorbent of the present invention can pass through below 60 ℃, under the stirring, to inject the soluble-salt of polyvalent metal in temperature in the outstanding muddy water solution of the hydrotalcite particulate that following formula (1) is represented, so that polyvalent metal compounds separates out manufacturing on the surface of hydrotalcite particulate,
Mg
1-xAl
x(OH)
2(Cl)
x-ny·(A
n-)
y·mH
2O (1)
In the formula, x is for satisfying the positive number of 0.15＜x＜0.34, A
N-Be Cl
-N valency anion in addition, y is a positive number, m is for satisfying the positive number of 0.1＜m＜0.7.
The hydrotalcite particulate is as illustrated in one in adsorbent.The hydrotalcite particulate is resulting particulate more than hydro-thermal Synthetic 2 under the temperature more than 100 ℃ hour preferably.
The content of the hydrotalcite particulate in the outstanding muddy water solution is preferably 2～10w/v%, more preferably 4～6w/v%.During deficiency 2w/v%, productivity is low, when surpassing 10w/v%, is difficult to make polyvalent metal compounds evenly to separate out on the hydrotalcite particle surface.Herein, so-called w/v% is that the ratio of the volume v (mL unit) of the water that will use in the weight w (g unit) of hydrotalcite in the outstanding muddy water solution and this suspension is represented to obtain with percentage.
The soluble-salt of polyvalent metal can be enumerated the soluble-salt of Zr (IV), Fe (III), Ce (III), Ce (IV), Ti (IV), V (V), Mn (II), Mn (III), Mn (IV), Mn (VI), Mn (VII), Cu (II), Co (II), Co (III), Mo (II), Mo (III), Mo (IV), Mo (V), Mo (VI), Ni (II), Ni (III) etc.
Wherein, at least a kind of metal soluble salt preferably from Fe (III), Zr (IV), Ti (IV), Ce (III) and Ce (IV), selecting.
Preferred chloride of soluble-salt or sulfate.Thereby, the soluble-salt preferred oxygen zirconium chloride of polyvalent metal, chlorination iron (III), titanium chloride (IV), cerous sulfate (IV), cerium chloride (III), vanadium oxydichloride (IV), manganese chloride (IV), copper chloride (II), cobalt chloride (II), oxychlorination molybdenum (III) and nickel chloride chloride or sulfate such as (II).If use replacement chlorides such as sulfate, it is some then to select adsorptivity to descend sometimes.The chloride or the sulfate of at least a kind of metal that the soluble-salt of polyvalent metal is preferably selected from Fe (III), Zr (IV), Ti (IV), Ce (III) and Ce (IV).
The temperature of injecting the outstanding muddy water solution of polyvalent metal soluble-salt is below 60 ℃, preferred 10～50 ℃, and more preferably 20～40 ℃.In manufacture method of the present invention, when stirring outstanding muddy water solution, inject the soluble-salt of polyvalent metal.
The X-ray diffractogram of the adsorbent that manufacturing method according to the invention obtains only provides the typical diffracted ray of HT, does not observe the oxide of polyvalent metal or the diffracted ray of hydroxide crystallization.This shows that polyvalent metal compounds is an amorphous state.
It is low that polyvalent metal ion generally precipitates pH, with the homogeneous reaction system of highly basic in, reaction forms hydroxide tempestuously, and crystallization even form oxide easily.But in manufacture method of the present invention, owing to the effect of bringing into play alkali as the HT of weak base and crystalline growth, so play a role as very soft alkali, the generation of polyvalent metal compounds is slowly carried out, and forms amorphous state easily.
And, as long as there is not polyvalent metal compounds in the HT microparticle surfaces, just can not solve problem of the present invention.In the present invention, the nuclear that the plane of crystal of HT particulate is separated out as precipitation and playing a role, thus amorphous polyvalent metal compounds is separated out at the HT microparticle surfaces efficiently.From these aspects, we can say that in the present invention HT plays a dual role for making the most suitable absorption phosphoric acid of amorphous state polyvalent metal compounds and arsenic.
Usually, at the aqueous solution that in the outstanding muddy water solution of HT particulate, injects the soluble-salt of polyvalent metal below 60 ℃, then separate out amorphous metal hydroxide or metal oxide or their compound, i.e. precipitating metal hydrous oxide at the HT microparticle surfaces.Thereby in the present invention, " polyvalent metal compounds " that so-called HT microparticle surfaces is separated out is the polyvalent metal hydrous oxide of amorphous state.In fact, during heat treated adsorbent of the present invention, having found that the weight that dehydration causes reduces, and adopts x-ray structure to resolve and can confirm to have generated crystallized oxide.
In the X-ray diffractogram of adsorbent of the present invention, do not observe the variation of the displacement, half breadth etc. of diffracted ray, hence one can see that, and former HT structure is maintained.Adsorbent of the present invention keep reason to the selective absorption performance of nitrate ion to be because the part of HT microparticle surfaces layer with the reaction of the soluble-salt aqueous solution of polyvalent metal in dissolved having consumed, but also keeping shape and the character of original HT in the remaining body.According to present supposition, the crystal structure that the HT that handled with the strong polyvalent metal soluble-salt aqueous solution of acidity causes owing to the acid dissolving destroys and other material is separated out in dissolving afterwards, so there is not adsorption capacity etc. in nitrate ion, but the method according to this invention can obtain the good adsorption performance.
In adsorbent of the present invention, the amorphous state polyvalent metal compounds is present in the surface of HT particulate.This fact HT particulate inside from the TEM photo present layer structure and the HT microparticle surfaces to be the phase with layer other of structure also can obtain confirming.Particularly, with respect to HT, the mol of amorphous state polyvalent metal compounds than hour, the HT microparticle surfaces is for covering the state of amorphous state polyvalent metal compounds equably.When the mol ratio of amorphous state polyvalent metal compounds increased, then the HT microparticle surfaces did not become just covering, also supported the state of graininess amorphous state polyvalent metal compounds.
Embodiment
Below, specify the manufacture method and the effect of adsorbent of the present invention based on embodiment.Device, the method used among the embodiment are as follows.
(1) average offspring mensuration directly
Adopt laser diffraction and scattering method particle size distribution device MT-3300 (day machine dress (strain) system)) measure.
(2) mensuration of BET method specific area
Full-automatic surperficial determinator マ Le チ ソ one Block-12 of 12 analytes that adopts soup shallow ア イ オ ニ Network ス (strain) to make is measured.
(3) observation of shape of particle
Adopt scanning electron microscope (SEM photo) to observe.
Method: accelerating potential 15kV, 20,000 times of operating distance 10mm, multiplying powers
Device: S-3000N (Hitachi)
(4) parsing of particle structure
The employing X-ray diffraction carries out.
Method: Cu-K α, angle (2 θ): 5～65 °, step-length: 0.02 °, sweep speed: 4 °/minute, tube voltage: 40kV, tube current: 20mV.
Device: RINT2200VX ray diffraction systems (motor of science (strain) system)
(5) constituent analysis
MgO, Al
2O
3, Fe
2O
3, CeO
2: adopt chelometry.
ZrO
2: adopt gravimetric method (mandelic acid zirconium precipitation)
TiO
2: adopt the UV absorption process
Cl: adopt Volhard method
CO
2: adopt method according to JIS R9101
(6) observation of HT particle surface
Adopt transmission electron microscope (TEM) to observe.
Method: accelerating potential 200kV (sample that causes for fear of the electron ray irradiation damages)
Device: JEM-3010 (NEC's (strain) system)
Adopt embodiment that the manufacture method of adsorbent of the present invention and the characteristic of adsorbent are described.Except specifying, reaction all is to carry out at normal temperatures, 1 grade of the reagent of medicine use and the pure medicine of light.
(synthesis example 1)
Prepare the mixed aqueous solution that 4.5L contains the aluminium chloride of the magnesium chloride of 1.194mol/L and 0.265mol/L (A liquid: Mg/Al=4.5) and the sodium hydrate aqueous solution (B liquid) of 4L 3.4mol/L respectively.
In the reactive tank of carry potential overflow pipe, add deionized water 500mL, injected 140 minutes according to the flow speed that constant displacement pump is determined as A liquid/B liquid=1.134/1.00, obtain containing the suspension that precipitates product while stir with Capacity Ratio.The suspension 750mL that obtains obtains reacting suspension A in 150 ℃ of following hydro-thermal reactions 8 hours.
Reaction suspension A filter, washing and 105 ℃ of dryings 18 hours.After using sample mill to pulverize, sieve, obtain adsorbent with the wire netting of 150 μ m.According to powder x-ray diffraction, composition analysis, particle size distribution as can be known, adsorbent is the HT particulate of Mg-Al-Cl system (Mg/Al=4.65).
(synthesis example 2)
After will reacting suspension A cool to room temperature, carry out following surface-coated processing operation, obtain adsorbent.2.84g reagent ZrOCl
28H
2O is dissolved in the 100mL deionized water, preparation ZrOCl
2Solution then, is added drop-wise among the above-mentioned reaction suspension A, reacts 1 hour.With product filter, washing, dry, pulverize and sieve, obtain adsorbent.The composition mol of the adsorbent that obtains is 4.79 than (Mg/Al).
(synthesis example 3)
Except with reagent ZrOCl
28H
2The quantitative change of O is beyond the 5.11g, and other adopts and synthesis example 2 same methods obtain adsorbent.The composition mol of the adsorbent that obtains is 4.51 than (Mg/Al).
(synthesis example 4)
Except with reagent ZrOCl
28H
2The quantitative change of O is beyond the 8.51g, and other adopts and synthesis example 2 same methods obtain adsorbent.The composition mol of the adsorbent that obtains is 4.39 than (Mg/Al).
(synthesis example 5)
Except with reagent ZrOCl
28H
2The quantitative change of O is beyond the 14.18g, and other adopts and synthesis example 2 same methods obtain adsorbent.The composition mol of the adsorbent that obtains compares Mg/Al=4.5.
(synthesis example 6)
Prepare the mixed aqueous solution that 5L contains the aluminium chloride of the magnesium chloride of 1.138mol/L and 0.285mol/L (C liquid: Mg/Al=4.0) and the above-mentioned B liquid of 4.3L respectively.Except making Capacity Ratio (C liquid/B liquid)=1.17/1.00, the method that other adopts and synthesis example 1 is same obtains reacting suspension B.And employing and synthesis example 1 same operation obtain adsorbent.According to powder x-ray diffraction, composition analysis, particle size distribution as can be known, adsorbent is the HT particulate of Mg-Al-Cl system (Mg/Al=4.03).
(synthesis example 7)
Behind the reaction suspension B cool to room temperature, make reagent ZrOCl
28H
2The quantitative change of O is 7.65g, uses reaction suspension B surrogate response suspension A, in addition carries out the processing operation same with synthesis example 2, obtains adsorbent.The composition mol of the adsorbent that obtains is 4.04 than (Mg/Al).
(synthesis example 8)
Except with reagent ZrOCl
28H
2The quantitative change of O is 15.3g, and reaction suspension B becomes beyond the reaction suspension D, and other adopts and synthesis example 2 same processing are operated, and obtains adsorbent.The composition mol of the adsorbent that obtains is 3.87 than (Mg/Al).
(comparative example 1)
At room temperature stir FeCl
36H
2In the time of O aqueous solution 650mL (92mmol), add MgO powder (460mmol), stirs after 40 minutes, make and precipitate the product suspension 170 ℃ of following hydro-thermal reactions 8 hours.After making hydro-thermal reaction liquid cooling but, filter, adopt the washing of 1L deionized water, drying is 20 hours under 105 ℃.After dry thing uses sample mill to pulverize, sieve, obtain adsorbent with the wire netting of 150 μ m.According to powder x-ray diffraction, composition analysis as can be known, adsorbent is the earth mantle lithotype stratiform complex hydroxide of Mg-Fe-Cl type (Mg/Fe=4.0).
(comparative example 2)
When at room temperature the mixed aqueous solution 300mL that contains magnesium chloride 0.28mol and aluminium chloride 0.07mol being stirred, inject above-mentioned B liquid 257mL, stirred 1 hour, obtain precipitating the product suspension.
When the precipitation product suspension that obtains is stirred, at room temperature add and contain reagent ZrOCl
28H
2The aqueous solution 100mL of O (0.07mol), then, 150 ℃ of following hydro-thermal reactions 8 hours.With the hydro-thermal reaction liquid cooling but, filter, washing, dry, pulverize and sieve after obtain adsorbent.According to powder x-ray diffraction, composition analysis as can be known, adsorbent is the HT and the crystalline zirconia of Mg-AI-Cl type (Mg/Al=3.65).
The characteristic of the adsorbent that obtains in synthesis example 1～8 and the comparative example 1～2 is as shown in table 1, the X-ray diffractogram of synthesis example 1 and 5, comparative example 1 and 2 adsorbent is shown in Figure 13,14,15 and 16, and the SEM photo of synthesis example 1,3 and 5 adsorbent is shown in Fig. 1,2 and 3.
By the B in the comparison sheet
0(006) and B
0(110) can know the c direction of principal axis of each adsorbent and the variation of the axial crystalline texture of ab.In addition, face is the face interval of being calculated by (003) face at interval.
By powder x-ray diffraction, composition analysis as can be known, synthesis example 2～5,7 and 8 adsorbent have the Mg-Al-Cl type HT particulate of amorphous state zirconium compounds for the surface.
Promptly, do not see that from x-ray diffractogram of powder HT existence is in addition arranged, but can confirm the existence of zirconium from chemical analysis results, and can confirm that from SEM photo and size distribution the particle footpath deviation of HT particulate, shape of particle in processings of the present invention front and back big variation do not take place, hence one can see that, and zirconium is enriched in the surface of HT particulate in amorphous compound.
By Fig. 1～3 (SEM photo) as can be known, the amount of zirconium compounds is when about scope below 12%, and the HT surface is covered equably by the amorphous state zirconium compounds.
(synthesis example 9)
When at room temperature mixed aqueous solution (Mg/Al=4.5) 363mL of the aluminium chloride of the magnesium chloride that contains 1.17mol/L and 0.259mol/L being stirred, inject the B liquid of above-mentioned 318mL, stir after 40 minutes, make the precipitation product 170 ℃ of following hydro-thermal reactions 8 hours, reaction suspension cool to room temperature with obtaining filters then, washes, drying.After using sample mill to pulverize, sieve, obtain adsorbent with the wire netting of 150 μ m.According to powder x-ray diffraction, composition analysis as can be known, adsorbent is the HT particulate of Mg-Al-Cl type (Mg/Al=4.5).
(synthesis example 10)
Except the amount that makes B liquid was 321mL, the operation that other is implemented and synthesis example 9 is same must be reacted suspension C.FeCl with 28.2mmol
36H
2O is dissolved in the 100mL deionized water, preparation FeCl
3The aqueous solution.In the reaction suspension C of 750mL, drip above-mentioned FeCl
3The aqueous solution reacted 1 hour.With the product filtering means dehydration, with deionized water 1L washing, 105 ℃ dry 20 hours down.After using sample mill to pulverize, sieve, obtain adsorbent with the wire netting of 150 μ m.The composition mol of the adsorbent that obtains is 4.19 than (Mg/Al).
(synthesis example 11)
Except making reagent FeCl
36H
2The amount of O is beyond the 47.0mmol and synthesis example 10 is handled operation equally, obtains adsorbent.The composition mol of the adsorbent that obtains is 3.84 than (Mg/Al).
(synthesis example 12)
Except making reagent FeCl
3The amount of 6H2O is beyond the 56.4mmol and synthesis example 10 is handled operation equally, obtains adsorbent.The composition mol of the adsorbent that obtains is 3.82 than (Mg/Al).
(synthesis example 13)
Except making reagent FeCl
36H
2The amount of O is beyond the 70.5mmol and synthesis example 10 is handled operation equally, obtains adsorbent.The composition mol of the adsorbent that obtains is 3.72 than (Mg/Al).
(synthesis example 14)
When at room temperature mixed aqueous solution (Mg/Al=4.5) 345mL of the aluminium chloride of the magnesium chloride that contains 1.187mol/L and 0.29mol/L being stirred, inject the B liquid of 304mL, stir after 40 minutes, make precipitation product suspension 170 ℃ of hydro-thermal reactions 8 hours, in addition, adopt and operation that synthesis example 9 is same, obtain adsorbent.According to powder x-ray diffraction, composition analysis as can be known, adsorbent is the HT particulate of Mg-Al-Cl type (Mg/Al=4.1).
(synthesis example 15)
Except the amount that makes B liquid is 313mL, implement and operation that synthesis example 9 is same, must react suspension D.In addition, replace with the reaction suspension D except reacting suspension C, other and synthesis example 10 are operated equally, obtain adsorbent.The composition mol of the adsorbent that obtains is 3.6 than (Mg/Al).
(synthesis example 16)
At room temperature, to Mg concentration be formulated as 1.36mol/L, contain the raw material of industry with the mixed aqueous solution (Mg/Al=5.0) of the aqueous solution of magnesium chloride and 1mol/L aluminum sulfate aqueous solution when stirring, inject above-mentioned B liquid and the synthesis example 9 of 326mL and operate equally, carry out hydro-thermal reaction.The reaction suspension E and the synthesis example 9 that obtain are operated equally, obtain adsorbent.According to powder x-ray diffraction, composition analysis, particle size distribution as can be known, the adsorbent that obtains is the HT particulate of, Mg-Al-Cl type (Mg/Al=4.94).
(synthesis example 17)
Except with reagent FeCl
36H
2The quantitative change of O is 54.0mmol, will react suspension C and replace with beyond the reaction suspension E, and other adopts and synthesis example 10 same processing are operated, and obtains adsorbent.The composition mol of the adsorbent that obtains is 4.19 than (Mg/Al).
(synthesis example 18)
Except with FeCl
36H
2The quantitative change of O is 81.0mmol, will react suspension C and replace with beyond the reaction suspension E, and other adopts and synthesis example 10 same processing are operated, and obtains adsorbent.The composition mol of the adsorbent that obtains is 3.66 than (Mg/Al).
(synthesis example 19)
Except with FeCl
36H
2The quantitative change of O is 90mmol, will react suspension C and replace with beyond the reaction suspension E, and other adopts and synthesis example 10 same processing are operated, and obtains adsorbent.The composition mol of the adsorbent that obtains is 3.48 than (Mg/Al).
(synthesis example 20)
Except with FeCl
36H
2The quantitative change of O is 141mmol, will react suspension C and replace with beyond the reaction suspension E, and other adopts and synthesis example 10 same processing are operated, and obtains adsorbent.The composition mol of the adsorbent that obtains is 2.52 than (Mg/Al).
(comparative example 3)
At room temperature to FeCl
36H
2O aqueous solution 650mL (104mmol) adds commercially available product Mg (OH) when stirring
2Powder (484mmol) stirred after 40 minutes, made the precipitation product 170 ℃ of following hydro-thermal reactions 8 hours.After hydro-thermal reaction liquid cooling but, filter, with deionized water 1L washing, 105 ℃ dry 20 hours down.After using sample mill to pulverize, sieve, obtain adsorbent with the wire netting of 150 μ m.According to powder x-ray diffraction, composition analysis as can be known, adsorbent is the stratiform complex hydroxide (earth mantle lithotype) of Mg-Fe-Cl type (Mg/Fe=3.65).
The character of the adsorbent that obtains in synthesis example 9～20 and the comparative example 3 is as shown in table 2, and the X-ray diffractogram of synthesis example 9 and 13 adsorbent is shown in Figure 17 and 18, and the SEM photo of synthesis example 9,10,13 and 19 adsorbent is shown in Fig. 4～7.
According to powder x-ray diffraction, composition analysis as can be known, synthesis example 10～13,15 and 17～20 adsorbent have the Mg-Al-Cl type HT particulate of amorphous state ferric iron compound for the surface.
Promptly, do not see that from x-ray diffractogram of powder HT existence is in addition arranged, can confirm ferric existence from chemical analysis results, in addition, can confirm that from SEM photo and size distribution big variation does not take place for the particle footpath deviation of HT particulate and shape of particle before and after processing of the present invention, hence one can see that, and ferric iron is enriched in the surface of HT particulate in amorphous compound.
By Fig. 4～6 (SEM photo) as can be known, the amount of ferric iron compound is when about scope below 15%, the surface of HT particulate evenly is covered by amorphous ferric iron compound, if but surpass this scope then will become particle shape ferric iron compound and also support in the state of HT microparticle surfaces.
(synthesis example 21)
At room temperature to the mixed aqueous solution (Mg/Al=4.5) of the liquor alumini chloridi 90.6mL of the magnesium chloride solution 204.4mL of 2.069mol/L and 1.038mol/L when stirring, inject the sodium hydrate aqueous solution 320mL of 3.38mol/L, stir after 30 minutes, make the precipitation product 170 ℃ of following hydro-thermal reactions 8 hours.
Reaction suspension F cool to room temperature with obtaining refilters, washes, drying.After using sample mill to pulverize, sieve, obtain adsorbent with the wire netting of 150 μ m.According to powder x-ray diffraction, composition analysis as can be known, adsorbent is the HT particulate of Mg-Al-Cl type (Mg/Al=4.42).
(synthesis example 22)
After the cooling, in the 1L container, add reaction suspension F, while stir the Ti (SO that drips 0.47mol/L
4)
2Solution 33mL (14mmol) reacted 1 hour.Product is filtered, with deionized water 1L washing, 105 ℃ dry 20 hours down.After using sample mill to pulverize, sieve, obtain adsorbent with the wire netting of 150 μ m.The composition mol of the adsorbent that obtains is 3.68 than (Mg/Al).
(synthesis example 23)
Except Ti (SO with 0.47mol/L
4)
2The dripping quantity of solution becomes beyond the 70mL, and other adopts and synthesis example 22 same processing are operated, and obtains adsorbent.The composition mol of the adsorbent that obtains is 3.31 than (Mg/Al).
(synthesis example 24)
Except Ti (SO with 0.47mol/L
4)
2The dripping quantity of solution becomes beyond the 100mL, and other adopts and synthesis example 22 same processing are operated, and obtains adsorbent.The composition mol of the adsorbent that obtains is 2.84 than (Mg/Al).
(synthesis example 25)
Except Ti (SO with 0.47mol/L
4)
2The dripping quantity of solution becomes beyond the 150mL, and other adopts and synthesis example 22 same processing are operated, and obtains adsorbent.The composition mol of the adsorbent that obtains is 2.11 than (Mg/Al).
(synthesis example 26)
To react suspension F and join in the 1L container, while stir the Ce (SO that drips 0.141mol/L
4)
2Solution 100mL (14.1mmol) reacted 1 hour.Then and synthesis example 22 handle equally, obtain adsorbent.The composition mol of the adsorbent that obtains is 4.37 than (Mg/Al).
(synthesis example 27)
Except dripping the Ce (SO of 0.217mol/L
4)
2Solution 130mL (28.2mmol) in addition, other and synthesis example 25 are operated equally, obtain adsorbent.The composition mol of the adsorbent that obtains is 4.00 than (Mg/Al).
The character of the adsorbent that obtains in the synthesis example 21～27 is as shown in table 3, and the X-ray diffractogram of synthesis example 23 and 25 adsorbent is shown in Figure 19 and 20, and the SEM photo of synthesis example 21,22,25,26 and 27 adsorbent is shown in Fig. 8～12.In addition, the TEM photo of synthesis example 21 and 27 adsorbent is shown in Figure 21 and 22.
By powder x-ray diffraction, composition analysis as can be known, the adsorbent of synthesis example 22～25 and synthesis example 26～27 is respectively the Mg-Al-Cl type HT particulate that the surface has amorphous state titanium-cuprum or cerium compound.
Promptly, do not see that by x-ray diffractogram of powder HT existence is in addition arranged, but can confirm the existence of titanium or cerium from chemical analysis results, can confirm that from SEM photo and size distribution big variation does not take place for the particle footpath deviation of HT particulate and shape of particle before and after processing of the present invention in addition, hence one can see that, and titanium or cerium are enriched in the surface of HT particulate in amorphous compound.(SEM photo) as can be known from Fig. 8～10, during the scope of the amount of titanium compound below about 3 weight %, the HT microparticle surfaces is evenly covered by amorphous titanium compound, also supports in the state of HT microparticle surfaces but then will become a part of particle shape titanium compound when surpassing about 17 weight %.In addition, from Figure 10,11 and 12 (SEM photo) as can be known, during the scope of the amount of cerium compound below about 12 weight %, the surface of HT particulate is evenly covered by amorphous cerium compound.
Figure 21 and 22 TEM photo that to be HT particulates that synthesis example 21 and 27 is obtained obtain from the direction observation of the layer that is parallel to the HT composition of getting its layer structure.From Figure 21 (TEM photo) as seen, carrying out inner from the HT particulate among the processing of the present invention HT before is a layer structure to the surface, but then, in the TEM photo of the adsorbent of the present invention shown in Figure 22, though HT particulate inside sustaining layer structure, its surface observation is to being cerium hydrous oxide micro-crystallization or amorphous image (do not have a layer structure-striped-strong contrast) by inference.This is the feature that the situation at other polyvalent metals such as zirconium, iron and titaniums is observed too.
Below, the effect of adsorbent of the present invention is described according to following examples.
(adsorption experiment example 1)
NaCl, NaNO to each 2mmol/L
3, Na
2CO
3, NaH
2PO
4, Na
2SO
4With mixed solution (pH=7.5) 50mL of the As (III) of 4ppm, adopt each the adsorbent 0.4g that obtains in synthesis example 1～27 (except that synthesis example 21) and the comparative example 1～3 to carry out adsorption experiment.After 2 hours, take 15mL, carry out Separation of Solid and Liquid with the filter of 0.2 μ m, each anion concentration adopts chromatography of ions to measure.Only the concentration of arsenic uses ICP-MS to measure.Distribution coefficient Kd obtains according to following formula.
Kd (mL/g)=anion adsorbance (mg/g)/anion concentration (mg/mL)
With the adsorption experiment result is that the Kd value that obtains of basic calculation is shown in table 4,5 and 6.NO in the table
3 -, HPO
4 2-, H
2AsO
3 -, SO
4 2-Refer to nitrate ion, phosphate anion, arsenic and sulfate ion respectively.
In addition, arsenic concentration with respect to the variation (adsorption rate) of time as shown in figure 23.
(adsorption experiment example 2)
With reference to the method for synthesis example 1, Mg/Al is than the adsorbent of the present invention that is 2,3,4,4.5 and 5 in preparation.Respectively each adsorbent is obtained distribution coefficient Kd with said method, show the result in Figure 24.
Distribution coefficient Kd value by synthesis example 9 and 14 (or 1 and 6) relatively and the nitrate ion of the adsorbent of comparative example 1 and 3 as can be known, Mg-Al-Cl type adsorbent of the present invention to the selection adsorptivity of nitrate ion than forming similar earth mantle lithotype adsorbent excellence in the past.
In addition, the distribution coefficient Kd value of the nitrate ion by synthesis example 14,9 that relatively synthesis condition is identical and 16 as can be known, (Mg/Al) ratio is that the Kd value is maximum in 4.5 the synthesis example 9, less than this than value be that the Kd value is lacked decline slightly in 4.0 the synthesis example 14, ratio is that the Kd value then reduces greatly in 4.9 the synthesis example 16.The ratio of (Mg/Al) is 4.5 o'clock as can be known, to the selection adsorptivity excellence of nitrate ion.From the experimental result of shown in Figure 22 other also is same, and the rising in the ratio of (Mg/Al) is about 2～4.5 scope of the distribution coefficient of nitrate ion is about 4.5 o'clock at this ratio, becomes the peak, and 5 o'clock, distribution coefficient descended rapidly.
ZrO from the synthesis example 1～5 of table 1
2The Fe of relation between the distribution coefficient of the arsenic of content and table 4 and the synthesis example of table 2 9～13
2O
3Relation between the distribution coefficient of the arsenic of content and table 5 as can be known, adsorbent of the present invention is a kind of in the high selectivity that keeps nitrate ion, the amount of the polyvalent metal compounds that the HT microparticle surfaces exists is many more, to the selection adsorptivity of arsenic and phosphate anion excellent more adsorbent just.Generally speaking, the Kd value increased near 1000 o'clock, was considered to the selected adsorbent of its ion.
Compare as can be known with the distribution coefficient that obtains in comparative example 1,2 and 3, for the amorphous state polyvalent metal compounds, when containing crystallinity multivalent metal hydroxides or oxide, not only poor to the selection adsorptivity of phosphate anion or arsenic, and also also poor to the selection adsorptivity of nitrate ion.That is, the Kd value that comprises above-mentioned 3 kinds of anionic Kd values of adsorbent of comparative example 2 of crystallinity zirconium compounds and synthesis example comprises the adsorbent excellence of the present invention of amorphous state zirconium compounds more as can be known.
In addition, from synthesis example 10～13,17～20 and 15 and above-mentioned 3 kinds of anionic Kd values of comparative example 1 and 3 more as can be known, contain the adsorbent excellence of the present invention of amorphous state ferric iron compound.
Equally as can be known, the HT particulate that the surface that the surface of the synthesis example 22～25 of table 3 has the HT particulate of amorphous state titanium-cuprum compound and a synthesis example 26～27 has an amorphous state cerium compound shown in the result of table 6, is the selected adsorbent of nitrate ion, arsenic and phosphate anion also.
As mentioned above as can be known, surface of the present invention has the HT of amorphous state polyvalent metal compounds and a kind of nitrate ion, arsenic and phosphate anion is shown the selected adsorbent of adsorptivity simultaneously.
The invention effect
Adsorbent of the present invention is big to the adsorption capacity of nitrate ion and arsenic.In addition, adsorbent of the present invention is big to the selectivity of nitrate ion and arsenic.In addition, adsorbent of the present invention less is subjected to the interference of counter anion can effectively remove nitrate ion and arsenic.In addition, adsorbent of the present invention safe to human body.The adsorbable phosphate anion of adsorbent of the present invention.
Thereby adsorbent of the present invention can simultaneously and effectively be removed nitrate ion, arsenic and phosphate anion with a kind of adsorbent in the solution of other anion coexistence.According to adsorbent of the present invention, can from general fresh water, adsorb and remove nitrate ion, arsenic and phosphate anion etc. to make safe drinking water.
Adsorbent of the present invention is in the absorption initial stage of arsenic, and adsorption capacity and adsorption rate are significantly big.It is irrealizable that this adsorption phenomena is that the surface does not have a hydrotalcite particulate simple substance institute of polyvalent metal compounds.
Manufacturing method according to the invention can be made adsorbent.
Arsenic comprises the ionic or neutral chemical seed that contains 5 valencys or 3 valency arsenic.Nitrate ion (NO
3 -) be by nitric acid and compound ionization thereof, decomposition and the main 1 valency anion that generates.
Phosphate anion comprises phosphate anion (PO
4 3-), phosphoric acid hydrogen radical ion (HPO
4 2-), dihydrogen phosphate ions (H
2PO
4-), gen-diphosphate (P
2O
7 4-), triphosphate (P
3O
10 5-) etc.
Industrial applicability
Adsorbent of the present invention can be used in water-purifying apparatus etc.
Claims (11)
1. adsorbent, what comprise that the hydrotalcite particulate of following formula (1) expression and surface thereof exist confirms as amorphous polyvalent metal compounds according to X-ray diffraction,
Mg
1-xAl
x(OH)
2(Cl)
x-ny·(A
n-)
y·mH
2O (1)
In the formula, x is for satisfying the positive number of 0.15＜x＜0.34, A
N-Be Cl
-N valency anion in addition, y is a positive number, m is for satisfying the positive number of 0.1＜m＜0.7.
2. the described adsorbent of claim 1, wherein, polyvalent metal compounds is oxide, hydroxide or their compound.
3. the described adsorbent of claim 1, wherein, polyvalent metal compounds is for being selected from the compound of at least a kind of metal among Zr (IV), Fe (III), Ti (IV) and the Ce (IV).
4. the described adsorbent of claim 1, wherein, the hydrotalcite particulate is the synthetic particulate that obtains of hydro-thermal under the temperature more than 100 ℃.
5. the described adsorbent of claim 1, wherein, the particulate of hydrotalcite particulate for more than hydro-thermal Synthetic 2 under 150～180 ℃ the temperature hour, obtaining.
6. the described adsorbent of claim 1 wherein, converts according to the oxide of polyvalent metal, and the amount of polyvalent metal compounds is 2～30 weight % with respect to the adsorbent total amount.
7. the described adsorbent of claim 1, wherein, in formula (1), x satisfies 0.16≤x≤0.20.
8. the described adsorbent of claim 1, wherein, in formula (1), (x-ny)/x satisfies 0.6≤(x-ny)/x≤1.0.
9. the described adsorbent of claim 1 wherein, has adsorptivity simultaneously to nitrate ion, phosphate anion and arsenic.
10. the manufacture method of adsorbent comprises: in temperature below 60 ℃, stir under, in the outstanding muddy water solution of the hydrotalcite particulate of following formula (1) expression, inject the soluble-salt of polyvalent metal, polyvalent metal compounds is separated out on the surface of hydrotalcite particulate,
Mg
1-xAl
x(OH)
2(Cl)
x-ny·(A
n-)
y·mH
2O (1)
In the formula, x is for satisfying the positive number of 0.15＜x＜0.34, A
N-Be Cl
-N valency anion in addition, y is a positive number, m is for satisfying the positive number of 0.1＜m＜0.7.
11. the described manufacture method of claim 10, wherein, the soluble-salt of polyvalent metal is for being selected from the chloride or the sulfate of at least a kind of metal among Fe (III), Zr (IV), Ti (IV), Ce (III) and the Ce (IV).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-021536 | 2008-01-31 | ||
| JP2008021536A JP5463525B2 (en) | 2008-01-31 | 2008-01-31 | Selective adsorbent and method for producing the same |
| PCT/JP2009/051918 WO2009096597A1 (en) | 2008-01-31 | 2009-01-29 | Selective adsorbent material, and method for production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101970099A true CN101970099A (en) | 2011-02-09 |
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| JP (1) | JP5463525B2 (en) |
| CN (1) | CN101970099A (en) |
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| WO (1) | WO2009096597A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032342A (en) * | 2015-06-18 | 2015-11-11 | 青岛科技大学 | Preparation method of stratiform bimetallic oxide sorbent capable of effectively removing low-concentrated phosphate radical |
| CN110201629A (en) * | 2019-07-11 | 2019-09-06 | 东华理工大学 | Ternary hydrotalcite adsorbent and its preparation method and application |
| CN116425135A (en) * | 2023-04-27 | 2023-07-14 | 成都理工大学 | Ferric hydroxide modified sodium zirconium phosphate and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI382842B (en) * | 2010-09-23 | 2013-01-21 | Univ Nat Chunghsing | Rapid method for preparing phosphrous binder and medicament contained thereof |
| US10301199B2 (en) | 2013-12-19 | 2019-05-28 | Industrial Technology Research Institute | Method for selective electrochemical removal of ions in water/wastewater |
| TWI547444B (en) | 2013-12-19 | 2016-09-01 | 財團法人工業技術研究院 | Electrode for electrochemical removal of phosphorus and apparatus, and method using the electrode |
| JP6664631B2 (en) * | 2014-08-11 | 2020-03-13 | 学校法人法政大学 | Phosphorus adsorbent, method for producing adsorbent, and adsorption method using adsorbent |
| JP6971135B2 (en) * | 2017-11-29 | 2021-11-24 | 東京エレクトロン株式会社 | Plasma processing equipment |
| KR20220073730A (en) | 2019-08-23 | 2022-06-03 | 고쿠리츠 다이가쿠 호우징 신슈 다이가쿠 | Layered double hydroxide crystal, anion adsorbent, and method for producing layered double hydroxide crystal |
| JP7264397B2 (en) * | 2019-11-13 | 2023-04-25 | 日機装株式会社 | Lactic acid adsorbent and method for removing lactic acid |
| EP4059601A4 (en) * | 2019-11-13 | 2024-01-03 | Nikkiso Co Ltd | Lactic acid absorber and method for removing lactic acid |
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| JP3190548B2 (en) * | 1994-10-27 | 2001-07-23 | 協和化学工業株式会社 | Resin composition and molded article |
| JPH08318131A (en) * | 1995-05-26 | 1996-12-03 | Mitsui Toatsu Chem Inc | Waste gas treating agent and treating method |
| JP2000233188A (en) * | 1999-02-15 | 2000-08-29 | Kaisui Kagaku Kenkyusho:Kk | Removing agent of selenium ion and arsenic ion, and use thereof |
| JPWO2006064568A1 (en) * | 2004-12-16 | 2008-06-12 | 東亞合成株式会社 | Anion exchanger and resin composition for sealing electronic parts using the same |
| JP4934962B2 (en) * | 2004-12-30 | 2012-05-23 | 堺化学工業株式会社 | Polycondensation catalyst for producing polyester and method for producing polyester using the same |
-
2008
- 2008-01-31 JP JP2008021536A patent/JP5463525B2/en active Active
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2009
- 2009-01-29 CN CN2009801036830A patent/CN101970099A/en active Pending
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032342A (en) * | 2015-06-18 | 2015-11-11 | 青岛科技大学 | Preparation method of stratiform bimetallic oxide sorbent capable of effectively removing low-concentrated phosphate radical |
| CN110201629A (en) * | 2019-07-11 | 2019-09-06 | 东华理工大学 | Ternary hydrotalcite adsorbent and its preparation method and application |
| CN116425135A (en) * | 2023-04-27 | 2023-07-14 | 成都理工大学 | Ferric hydroxide modified sodium zirconium phosphate and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009096597A1 (en) | 2009-08-06 |
| JP2009178682A (en) | 2009-08-13 |
| TW200942323A (en) | 2009-10-16 |
| JP5463525B2 (en) | 2014-04-09 |
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