CN102302926A - Composite modified layered double-metal hydroxide and method for preparing same - Google Patents
Composite modified layered double-metal hydroxide and method for preparing same Download PDFInfo
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- CN102302926A CN102302926A CN 201110166964 CN201110166964A CN102302926A CN 102302926 A CN102302926 A CN 102302926A CN 201110166964 CN201110166964 CN 201110166964 CN 201110166964 A CN201110166964 A CN 201110166964A CN 102302926 A CN102302926 A CN 102302926A
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Abstract
The invention belongs to the technical field of novel materials and water pollution treatment agents and particularly relates to a composite modified layered double-metal hydroxide and a method for preparing the same. The composite modified layered double-metal hydroxide and the method for preparing the same mainly solve the technical problem that heavy metal cations and organic pollutants in sewage cannot be cooperatively adsorbed by a layered double-metal hydroxide material. The composite modified layered double-metal hydroxide provided by the invention is made by commonly modifying a layered double-metal hydroxide through an anionic surfactant and a metal complexing agent. According to the invention, the insertion amount of both the surfactant and the metal complexing agent is large, and the surfactant and the metal complexing agent are evenly inserted between layers of the layered double-metal hydroxide through a structural reconstruction method and an ion-exchange method step by step so as to realize composite modification.
Description
Technical field
The invention belongs to new material and water and pollute the inorganic agent technical field, be specifically related to a kind of composite modified stratiform double-metal hydroxide and preparation method thereof.
Background technology
China has a large population, water resource lacks, and water resources ownership per capita is 1/4 of a world average level only, is one of 13 poor-water states in the world.A large amount of town domestic sewages and various industrial wastewater are unprocessed and directly discharge or do not have a qualified discharge; Make underground water receive pollution to a certain degree; Deteriorating water quality; And the trend that increases the weight of is year by year arranged; The water that is on the rise pollutes, and has not only reduced the function of use of water body, the contradiction of further having aggravated shortage of water resources; The strategy of sustainable development to China is implementing has been brought serious negative effect, but also seriously threatens city dweller's safe drinking water and the people's health.In real work, focus on after various industrial wastewaters are normal mixed, cause containing simultaneously in the waste water a large amount of heavy metals and various organic pollution.
What processing waste water was commonly used at present is absorption method; Its great advantage is that equipment is simple, easy to operate; The saturated renewable use in back of adsorbents adsorb; Adsorbate also can be recycled; But present adsorbents adsorb function singleness promptly can only be adsorbed a kind of in heavy metal or the organic pollution, and two kinds of pollutants are simultaneously and deposit often in the water; For this reason, be badly in need of exploitation can be simultaneously the effectively new material and the new technology of heavy metal and organic pollution in the adsorption treatment waste water.
The hydroxide with hydrotalcite layered structure that the laminated type bimetal hydroxide compound is made up of bivalent metal ion and trivalent metal ion is claimed mixed metal hydroxides again; The laminated type bimetal hydroxide compound has the shepardite lamellar structure; Laminate is owing to trivalent metal ion isomorphous substitution bivalent metal ion has positive charge; Anionic electric charge of the object that interlayer can exchange and laminate positive charge balance; Make the laminated type bimetal hydroxide compound be electroneutral; The laminated type bimetal hydroxide compound has bigger anion-exchange capacity (AEC; 2-3meq/g); Acceptant object anion; Therefore the metal that can be used to exist with the anion form in the adsorbed water body is (like Cr (VI); As (V), Se (IV) etc.) and organic pollution.
Summary of the invention
The present invention is primarily aimed at that heavy metal cation and organic pollution can not be by the technical problems of the collaborative absorption of stratiform bimetal hydroxide laminate material in the sewage; A kind of composite modified stratiform bimetal hydroxide compound and preparation method thereof is provided, has can be used for environmental wastewater and handle.
The present invention for realizing the technical scheme that above-mentioned purpose is taked is:
The composite modified stratiform double-metal hydroxide of the present invention be by anion surfactant and metal chelating agent to layered double hydroxide common modification process;
The general structure of wherein said layered double hydroxide is: [M (II)
(1-x)M (III)
x(OH)
2] (A)
X/nMH
2O, wherein: M (II) is a bivalent metal ion, and M (III) is a trivalent metal ion, and A is-n valency anion, n=1～2, x is the molal quantity of M in every mole of layered double hydroxide (III), x=0.2～0.4; M is the molal quantity of the interlayer crystallization water in every mole of layered double hydroxide, m=0.5～6;
The general formula of said composite modified stratiform double-metal hydroxide is: [M (II)
(1-x)M (III)
x(OH)
2] (A)
a(SAA)
b(Complexation)
cMH
2O, wherein: M (II) is a bivalent metal ion; M (III) is a trivalent metal ion; A is-n valency anion; N=1～2; X is the molal quantity of M (III) in every mole of modified layered double-metal hydroxide, x=0.35～0.51; M=0.5～6; SAA is the anion of anion surfactant, and Complexation is the metal chelating agent anion, a=0.05～0.40; B=0.03～0.17; C=0.02～0.14.
The preparation method of the composite modified stratiform double-metal hydroxide of the present invention may further comprise the steps:
1) earlier with the layered double hydroxide calcining, calcined product is scattered in the anionic surfactant solution, the pH value of regulation system is 9～11 again, under nitrogen protection, the stirrings 10～72 hours down of 20～70 ℃ of constant temperature, processes dispersion;
2) metal chelating agent is added in the dispersion, regulating pH value is 5.5～6.5, and under nitrogen protection, constant temperature stirred 3～12 hours down for 50～80 ℃, suction filtration, washing, dry sediment get composite modified stratiform double-metal hydroxide.
Preferred bivalent metal ion M (II) is Mg in the composite modified stratiform double-metal hydroxide of the present invention
2+, Zn
2+, Fe
2+, Ni
2+Or Ca
2+Trivalent metal ion M (III) is Al
3+, Cr
3+, Fe
3+Or Co
3+-n valency anion A is Cl
-, OH
-, NO
3 -, CO
3 2-Or SO
4 2-Anion surfactant is lauryl sodium sulfate C
12H
25SO
4Na; Metal chelating agent is disodium ethylene diamine tetraacetate C
10H
14N
2Na
2O
82H
2O.
Preferred, in the layered double-metal hydroxide, M (II) is Mg
2+M (III) is Al
3+A is Cl
-
Further, bivalent metal ion of the present invention is 2～4: 1 with the amount of substance ratio of trivalent metal ion.
Layered double hydroxide calcining heat according to the invention is 400～500 ℃.
The calcined product of layered double-metal hydroxide is 1: 0.25～1 with the ratio of the amount of substance of anion surfactant.
The calcined product of layered double-metal hydroxide is 1: 0.25～1 with the ratio of the amount of substance of metal chelating agent.
The temperature of said dry sediment is 40～80 ℃.
The present invention utilizes D/max-γ Type B X-ray powder diffraction appearance; Under the condition of 0.2 ° of voltage 40kV, electric current 100mA, Cu target K α radiation, 4 °/min of sweep speed, scanning step; In 2 ° of-70 ° of scopes, record the X-ray powder diffraction of layered double hydroxide of the present invention and modified layered double-metal hydroxide, through same diffraction maximum (d before and after the modification in the collection of illustrative plates
003) displacement, prove that anion surfactant anion and metal chelating agent anion among the present invention have inserted the interlayer of layered double hydroxide.
Simultaneously, the present invention also utilizes Nicolet USA 5DX fourier-transform infrared absorption spectrometer at resolution ratio 1cm
-1Condition under, detect at 400-4000cm
-1The layered double hydroxide in the scope and the infrared spectrum of modified layered double-metal hydroxide: the existence form that compares the provable modified layered double-metal hydroxide interlayer anion of difference of the two collection of illustrative plates.3600-3500cm
-1Scope is the hydrogen bond stretching vibration absworption peak of hydroxyl on the laminate; 3000cm
-1The place is the hydrogen bond absworption peak between intermediary water and other anion; 1800-1000cm
-1Scope is the stretching vibration peak of interlayer anion; 1000-400cm
-1Scope is the vibration absorption peak that metal cation and oxygen form covalent bond.
The content of metallic element Mg and Al in layered double hydroxide of the present invention and the modified layered double-metal hydroxide (wt%) measure through IRIS ADVANTAGE type inductive coupling plasma emission spectrograph by mass percent; C, H, N, S content (wt%) are measured through Vario ELIII type elemental analyser.Amount (n) by the wt% countable entity matter of each element.Layered double hydroxide [Mg
(1-x)Al
x(OH)
2] (Cl)
xMH
2O or modified layered double-metal hydroxide [Mg
(1-x)Al
x(OH)
2] (Cl)
a(C
12H
25SO
4)
b(C
10H
14N
2O
8)
cMH
2The x value can be by n (Mg): n (Al)=2 (1-x) among the O: x draws; [Mg
(1-x)Al
x(OH)
2] (Cl)
xMH
2M=[n among the O (H) (1-x)-2n (Mg)]/(2n (Mg)); [Mg
(1-x)Al
x(OH)
2] (Cl)
a(C
12H
25SO
4)
b(C
10H
14N
2O
8)
cMH
2C=n among the O (N) (1-x)/(2n (Mg)), b=n (S) (1-x)/n (Mg), a=x-b-2c, m=[n (H) is n (Mg) (1-x)-(25b+14c+2)]/(2n (Mg)).
The present invention is the main body with synthetic layered double hydroxide easy, that have layer structure, band structure positive charge; With anion surfactant and metal chelating agent is object; Prepared composite modified stratiform double-metal hydroxide; Can utilize the nonpolar action of surfactant to dissolve organic pollution in the sewage; Utilize the special stability of metal chelating agent effectively to remove heavy metal ion in the water, thereby realize of collaborative, the effectively absorption of composite modified stratiform double-metal hydroxide heavy metal in the water body and organic pollution.The modified layered double-metal hydroxide method of preparation NEW TYPE OF COMPOSITE is simple among the present invention, and cost is lower, has played positive role for layered double hydroxide in the application aspect the water treatment.Therefore; Compared with prior art the present invention has following beneficial effect: 1, existing modification to layered double hydroxide is single modification (at layered double hydroxide interlayer or insertion surfactant or insertion metal chelating agent); And the present invention proposes surfactant and metal chelating agent are all inserted the layered double hydroxide interlayer, realize composite modified through structural remodeling method and ion-exchange substep; 2, the insertion amount of surfactant of the present invention and metal chelating agent is all bigger, and surfactant and metal chelating agent anion molal quantity can reach 0.17 and 0.14 respectively in every mole of composite modified stratiform double-metal hydroxide; 3, preparation method of the present invention is simple, and cost is low.
Description of drawings
Fig. 1 is the powder x-ray diffraction figure of modification front and back laminated type bimetal hydroxide compound among the embodiment of the invention 1-3, and wherein a is the powder x-ray diffraction figure of embodiment 1 laminate bimetal hydroxide compound; B is the powder x-ray diffraction figure of embodiment 2 laminate bimetal hydroxide compounds; C is the powder x-ray diffraction figure of embodiment 3 laminate bimetal hydroxide compounds; D is the powder x-ray diffraction figure of modified layered bimetal hydroxide compound among the embodiment 1; E is the powder x-ray diffraction figure of modified layered bimetal hydroxide compound among the embodiment 2; F is the powder x-ray diffraction spectrogram of modified layered bimetal hydroxide compound among the embodiment 3;
Fig. 2 is the infrared spectrum of modification front and back laminated type bimetal hydroxide compound among the embodiment of the invention 1-3, and wherein a is the infrared spectrum of embodiment 1 laminate bimetal hydroxide compound; B is the infrared spectrum of embodiment 2 laminate bimetal hydroxide compounds; C is the infrared spectrum of embodiment 3 laminate bimetal hydroxide compounds; D is the infrared spectrum of modified layered bimetal hydroxide compound among the embodiment 1; E is the infrared spectrum of modified layered bimetal hydroxide compound among the embodiment 2; F is the infrared spectrum of modified layered bimetal hydroxide compound among the embodiment 3.
The specific embodiment
Embodiment 1
1) with layered double hydroxide [Mg
0.78Al
0.22(OH)
2] (Cl)
0.220.5H
2O gets calcined product 300mg and is scattered in the lauryl sodium sulfate (C that 30mL concentration is 0.1mol/L 500 ℃ of calcinings
12H
25SO
4Na, SDS) in the aqueous solution, using the NaOH solution regulation system pH value of 0.01mol/L is 9, under nitrogen protection, the stirring 42 hours down of 70 ℃ of constant temperature, processes dispersion;
2) get the disodium ethylene diamine tetraacetate (C that concentration is 0.06mol/L
10H
14N
2Na
2O
82H
2O, Na
2-EDTA) solution 33mL adds in the dispersion, and using the HCl of 0.01mol/L to regulate pH value is 6.5, under nitrogen protection, the stirring 8 hours down of 80 ℃ of constant temperature, suction filtration, washing, sediment dries to constant weight at 80 ℃, promptly gets composite modified stratiform double-metal hydroxide [Mg
0.64Al
0.36(OH)
2] (Cl)
0.1(C
12H
25SO
4)
0.12(C
10H
14N
2O
8)
0.070.7H
2O.
A is the powder x-ray diffraction figure of present embodiment laminated type bimetal hydroxide compound among Fig. 1, and d is the powder x-ray diffraction figure of modified layered bimetal hydroxide compound in the present embodiment; Relatively a and d curve can be known, the 0.772nm of the interlamellar spacing of layered double hydroxide before by modification becomes 2.752nm after the modification (with C
12H
25SO
4 -Molecular length 2.23nm+ laminate thickness 0.48nm=2.71nm basically identical) and 1.343nm (with C
10H
14N
2O
8 2-Molecular length 0.91nm+ laminate thickness 0.48nm=1.39nm basically identical), illustrate in the modified layered bimetal hydroxide compound and inserted C
12H
25SO
4 -And C
10H
14N
2O
8 2-
A is the infrared spectrum of present embodiment laminate bimetal hydroxide compound among Fig. 2, and d is the infrared spectrum of modified layered bimetal hydroxide compound in the present embodiment; Relatively a and d curve can be known, have increased by 2850～2965cm after the layered double hydroxide modification
-1Absworption peak (CH
2The contraction vibration peak) ,～1229cm
-1Absworption peak (SO
4Vibration peak) and 1400～1600cm
-1Absworption peak (COO
-The contraction vibration peak), illustrating in the modified layered bimetal hydroxide compound has increased C
12H
25SO
4 -And C
10H
14N
2O
8 2-Ion.
Embodiment 2
1) with layered double hydroxide [Mg
0.65Al
0.35(OH)
2] (Cl)
0.352.7H
2O gets calcined product 280mg and is scattered in the lauryl sodium sulfate (C that 30mL concentration is 0.15mol/L 450 ℃ of calcinings
12H
25SO
4Na, SDS) in the aqueous solution, using the NaOH solution regulation system pH value of 0.01mol/L is 9.5, under nitrogen protection, the stirring 52 hours down of 50 ℃ of constant temperature, processes dispersion;
2) get the disodium ethylene diamine tetraacetate (C that concentration is 0.2mol/L
10H
14N
2Na
2O
82H
2O, Na
2-EDTA) solution 30mL adds in the dispersion, and using the HCl of 0.01mol/L to regulate pH value is 6, under nitrogen protection, the stirring 4 hours down of 50 ℃ of constant temperature, suction filtration, washing, sediment dries to constant weight at 60 ℃, promptly gets composite modified stratiform double-metal hydroxide [Mg
0.49Al
0.51(OH)
2] (Cl)
0.1(C
12H
25SO
4)
0.17(C
10H
14N
2O
8)
0.122.3H
2O.
B is the powder x-ray diffraction figure of present embodiment laminated type bimetal hydroxide compound among Fig. 1, and e is the powder x-ray diffraction figure of modified layered bimetal hydroxide compound in the present embodiment; Relatively b and e curve can be known, the 0.772nm of the interlamellar spacing of layered double hydroxide before by modification becomes 2.984nm after the modification (with C
12H
25SO
4 -Molecular length 2.23nm+ laminate thickness 0.48nm=2.71nm basically identical) and 1.390nm (with C
10H
14N
2O
8 2-Molecular length 0.91nm+ laminate thickness 0.48nm=1.39nm is consistent), illustrate in the modified layered bimetal hydroxide compound and inserted C
12H
25SO
4 -And C
10H
14N
2O
8 2-
B is the infrared spectrum of present embodiment laminate bimetal hydroxide compound among Fig. 2, and e is the infrared spectrum of modified layered bimetal hydroxide compound in the present embodiment; Relatively b and e curve can be known, have increased by 2850～2965cm after the layered double hydroxide modification
-1Absworption peak (CH
2The contraction vibration peak) ,～1229cm
-1Absworption peak (SO
4Vibration peak) and 1400～1600cm
-1Absworption peak (COO
-The contraction vibration peak), illustrating in the modified layered bimetal hydroxide compound has increased C
12H
25SO
4 -And C
10H
14N
2O
8 2-Ion.
Embodiment 3
1) with layered double hydroxide [Mg
0.68Al
0.32(OH)
2] (Cl)
0.323H
2O gets calcined product 250mg and is scattered in the lauryl sodium sulfate (C that 30mL concentration is 0.1mol/L 500 ℃ of calcinings
12H
25SO
4Na, SDS) in the aqueous solution, using the NaOH solution regulation system pH value of 0.01mol/L is 10, under nitrogen protection, the stirring 48 hours down of 30 ℃ of constant temperature, processes dispersion;
2) get the disodium ethylene diamine tetraacetate (C that concentration is 0.2mol/L
10H
14N
2Na
2O
82H
2O, Na
2-EDTA) solution 25mL adds in the dispersion, and using the HCl of 0.01mol/L to regulate pH value is 5.5, under nitrogen protection, the stirring 6 hours down of 70 ℃ of constant temperature, suction filtration, washing, sediment dries to constant weight at 55 ℃, promptly gets composite modified stratiform double-metal hydroxide [Mg
0.52Al
0.48(OH)
2] (Cl)
0.07(C
12H
25SO
4)
0.13(C
10H
14N
2O
8)
0.143.5H
2O.
C is the powder x-ray diffraction figure of present embodiment laminated type bimetal hydroxide compound among Fig. 1, and f is the powder x-ray diffraction figure of modified layered bimetal hydroxide compound in the present embodiment; Relatively c and f curve can be known, the 0.767nm of the interlamellar spacing of layered double hydroxide before by modification becomes 2.752nm after the modification (with C
12H
25SO
4 -Molecular length 2.23nm+ laminate thickness 0.48nm=2.71nm basically identical) and 1.401nm (with C
10H
14N
2O
8 2-Molecular length 0.91nm+ laminate thickness 0.48nm=1.39nm basically identical), illustrate in the modified layered bimetal hydroxide compound and inserted C
12H
25SO
4 -And C
10H
14N
2O
8 2-
C is the infrared spectrum of present embodiment laminate bimetal hydroxide compound among Fig. 2, and f is the infrared spectrum of modified layered bimetal hydroxide compound in the present embodiment; Relatively c and f curve can be known, have increased by 2850～2965cm after the layered double hydroxide modification
-1Absworption peak (the contraction vibration peak of CH2) ,～1229cm
-1Absworption peak (SO
4Vibration peak) and 1400～1600cm
-1Absworption peak (the contraction vibration peak of COO-), illustrating in the modified layered bimetal hydroxide compound has increased C
12H
25SO
4 -And C
10H
14N
2O
8 2-Ion.
Claims (8)
1. composite modified stratiform double-metal hydroxide, it is characterized in that by anion surfactant and metal chelating agent to layered double hydroxide common modification process;
Wherein: the general formula of said composite modified stratiform double-metal hydroxide is: [M (II)
(1-x)M (III)
x(OH)
2] (A)
a(SAA)
b(Complexation)
cMH
2O, wherein: M (II) is a bivalent metal ion; M (III) is a trivalent metal ion; A is-n valency anion; N=1～2; X is the molal quantity of M (III) in every mole of modified layered double-metal hydroxide, x=0.35～0.51; M=0.5～6; SAA is the anion of anion surfactant, and Complexation is the metal chelating agent anion, a=0.05～0.40; B=0.03～0.17; C=0.02～0.14.
2. the preparation method of the described composite modified stratiform double-metal hydroxide of claim 1 is characterized in that may further comprise the steps:
1) earlier with the layered double hydroxide calcining, calcined product is scattered in the anionic surfactant solution, the pH value of regulation system is 9～11 again, under nitrogen protection, the stirrings 10～72 hours down of 20～70 ℃ of constant temperature, processes dispersion;
2) metal chelating agent is added in the dispersion, regulating pH value is 5.5～6.5, and under nitrogen protection, constant temperature stirred 3～12 hours down for 50～80 ℃, suction filtration, washing, dry sediment get composite modified stratiform double-metal hydroxide.
3. a kind of composite modified stratiform double-metal hydroxide according to claim 1 is characterized in that described bivalent metal ion M (II) is Mg
2+, Zn
2+, Fe
2+, Ni
2+Or Ca
2+Described trivalent metal ion M (III) is Al
3+, Cr
3+, Fe
3+, or Co
3+Described-n valency anion A is Cl
-, OH
-, NO
3 -, CO
3 2-Or SO
4 2-Said anion surfactant is lauryl sodium sulfate C
12H
25SO
4Na; Said metal chelating agent is disodium ethylene diamine tetraacetate C
10H
14N
2Na
2O
82H
2O.
4. a kind of composite modified stratiform double-metal hydroxide according to claim 1 is characterized in that the described bivalent metal ion and the amount of substance ratio of trivalent metal ion are 2～4: 1.
5. the preparation method of a kind of composite modified stratiform double-metal hydroxide according to claim 2 is characterized in that described layered double hydroxide calcining heat is 400～500 ℃.
6. the preparation method of a kind of composite modified stratiform double-metal hydroxide according to claim 2, the calcined product that it is characterized in that described layered double hydroxide is 1: 0.25～1 with the ratio of the amount of substance of anion surfactant.
7. the preparation method of a kind of composite modified stratiform double-metal hydroxide according to claim 2, the calcined product that it is characterized in that described layered double hydroxide is 1: 0.25～1 with the ratio of the amount of substance of metal chelating agent.
8. the preparation method of a kind of composite modified stratiform double-metal hydroxide according to claim 2, the temperature that it is characterized in that described dry sediment is 40～80 ℃.
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| CN112316924A (en) * | 2020-10-20 | 2021-02-05 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Coal gangue-based porous composite material and preparation method and application thereof |
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