CN102671640B - Hydrated titanium dioxide-persimmon tannin acrylic resin compound sorbent, preparation method thereof and application thereof - Google Patents
Hydrated titanium dioxide-persimmon tannin acrylic resin compound sorbent, preparation method thereof and application thereof Download PDFInfo
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- CN102671640B CN102671640B CN201210165723.8A CN201210165723A CN102671640B CN 102671640 B CN102671640 B CN 102671640B CN 201210165723 A CN201210165723 A CN 201210165723A CN 102671640 B CN102671640 B CN 102671640B
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- titanium dioxide
- hydrated titanium
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- persimmon tannin
- silane coupler
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Abstract
The invention provides a hydrated titanium dioxide-persimmon tannin acrylic resin compound sorbent, a preparation method thereof and the application thereof, wherein, the preparation method of the compound sorbent comprises the steps as follows: silane coupling agents are added in water and is stirred for dissolution, then hydrated titanium dioxide is added and stirred, reaction is performed for 12 hours, and then centrifugation, washing and drying are carried out so as to obtain the modified hydrated titanium dioxide; mixed solution containing sodium acrylate is prepared by mixing N,N'-methylene-bisacrylamide, ammonium persulfate and persimmon tannin solution; n-hexane, anionic surface active agents and the hydrated titanium dioxide that is modified through the silane coupling agents are added in a reaction kettle, reaction is performed for 10 to 20 minutes under the conditions that nitrogen is pumped in and stirring is carried out, then mixed solution is added, stirring is performed, the temperature increases to 75 DEG C, and reaction is performed for 1.5 hours under the stirring condition; and n-hexane is removed through filtration, and vacuum drying is carried out, so as to obtain the hydrated titanium dioxide-persimmon tannin acrylic resin compound sorbent. The compound sorbent with low cost has the compound inorganic-organic advantages, achieves a good pb2 plus adsorption effect, and achieves simple synthesis technological process and high polymerization speed, and is easy to dry.
Description
Technical field
The present invention relates to lead waste water processing composite, relate in particular to a kind of hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent, its preparation method and application thereof.
Background technology
Heavy metal ion has very large toxicity, the hard-decomposed and interior enriching of organism, and can threaten by the circulation of food chain the health of human body.Although some trace elements is useful to human body, most of heavy metal is not that human life activity is required, and can cause very large injury to human body over certain concentration.In GB GB8978-88 < < integrated wastewater discharge standard > >, just the highest permission concentration of emission of heavy metal has been carried out to clear and definite regulation.And be early well known as toxicity and the harm of strong pollutant lead, therefore, for the processing of lead waste water, caused widely and paid close attention to.
Because heavy metal ion has hard-decomposedly, therefore, for the improvement of heavy metal, can only adopt the location of shifting them and the method that changes their physical and chemical state.Under years of researches, existing chemical precipitation method, hyperfiltration, electrolysis, ion-exchange and biosorption process etc.Wherein, absorption method has efficiently, easy to operate and can recycled for multiple times etc. advantage, be widely used in the absorption of heavy metal ion.And in recent years, biological treatment have cost low, easy, can not bring the new advantages such as pollution, also in the improvement of heavy metal wastewater thereby, obtained good application.
Summary of the invention
The object of this invention is to provide a kind of lead waste water and process hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent, its preparation method and the application thereof of the excellent adsorption of use.
Technical scheme of the present invention is as follows:
A preparation method for hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent, it comprises the following steps:
1) surface treatment of hydrated titanium dioxide: by hydrated titanium dioxide: the mass ratio of silane coupler is that 1:0.15-2.4 chooses silane coupler and hydrated titanium dioxide is standby, silane coupler is added to stirring and dissolving in water, then add centrifugal after hydrated titanium dioxide stirring reaction 12h, washing, dry, obtain through silane coupler modified hydrated titanium dioxide;
2) get the raw materials ready: according to n-hexane: anion surfactant: acrylic acid mass ratio is that 100-200:18-36:13-50 chooses n-hexane, anion surfactant and acrylic acid, according to above-mentioned through silane coupler modified hydrated titanium dioxide: persimmon tannin solution: ammonium persulfate: N-N methylene-bisacrylamide: it is standby that acrylic acid mass ratio is that 4-12:46:0.26:0.07:100 chooses through silane coupler modified hydrated titanium dioxide, persimmon tannin solution, ammonium persulfate and N-N methylene-bisacrylamide;
3) the mixed liquor preparation that contains PAA: preparation sodium hydroxide solution, in ice-water bath, described sodium hydroxide solution is joined in acrylic acid, stir, make acrylic acid degree of neutralization remain on 70%, add again N, N '-methylene-bisacrylamide, ammonium persulfate and persimmon tannin solution, constantly stir it mixed, and obtains the mixed liquor that contains PAA;
4) synthetic: by n-hexane, anion surfactant with add in reactor through silane coupler modified hydrated titanium dioxide, react 10～20 minutes passing under nitrogen and stirring condition, then add the resulting mixed liquor of step (3), stir, be warmed up to 75 ° of C stirring reaction 1.5h;
5) material step 4) being obtained is poured out, and filters n-hexane, and vacuum drying obtains hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent.
In such scheme, described silane coupler is γ-methacryloxypropyl trimethoxy silane.
In such scheme, the hydrated titanium dioxide in described step 1): the mass ratio of silane coupler is 1:0.3.
In such scheme, the centrifugation rate in described step 1) is 3500r/min, and centrifugation time is 20min.
In such scheme, the baking temperature in described step 1) is 80 ℃, dry under vacuum condition.
In such scheme, the stir speed (S.S.) in described step 4) is 450 revs/min.
In such scheme, the preparation method of described persimmon tannin solution comprises the steps: after the blue or green persimmon fragmentation of plucking, in blue or green persimmon: the ratio of mass ratio=1:0.5～10 of distilled water was soaked after two weeks, press again juice, filtrate is after vacuum filtration, spontaneous fermentation 1～2 year, obtains bronzing persimmon tannin solution.
In such scheme, described anion surfactant is polyoxyethylene alkyl ether sulfate salt.
A kind of hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent being prepared by said method.
The application of a kind of hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent being prepared by said method in lead waste water is processed.
Principle of the present invention is: the present invention adopts conversed phase micro emulsion copolymerization method to synthesize this compound adsorbent, persimmon tannin is grafted in acrylic resin polymer architecture, in γ-methacryloxypropyl trimethoxy silane structure, contain two keys, with this silane coupler, hydrated titanium dioxide surface is coated, by reversed-phase polymerization method, allow two keys in two keys in coupling agent and acrylic acid carry out polymerisation, thereby form hydrated titanium dioxide-persimmon tannin acrylic resin complex microsphere.
Beneficial effect of the present invention is:
1. synthesize in the raw material of this compound adsorbent, the abundant raw material of first synthetic hydrated titanium dioxide, cheap, while doing adsorbent use, pH value scope is wide; Secondly, persimmon tannin has very strong price reduction adsorption capacity to metal ion, has low cost, environmental protection and adsorbs the advantages such as efficient; Therefore greatly reduce the cost of this adsorbent.
2. this compound adsorbent has the advantage of inorganic-organic hybrid, for to pb
2+adsorption experiment, respond well.
3. synthesis technique flow process of the present invention is simple, and polymerization speed is fast, and product is easily dry.
The specific embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to the following examples.
Embodiment 1:
A preparation method for hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent, it comprises the following steps:
1) surface treatment of hydrated titanium dioxide: by hydrated titanium dioxide: the mass ratio of silane coupler is that 1:0.15 chooses silane coupler and hydrated titanium dioxide is standby, silane coupler is added to stirring and dissolving in water, then add hydrated titanium dioxide stirring reaction 12h, centrifugal (3500r/min, 20min), washing, 80 ℃ of vacuum drying, obtain through silane coupler modified hydrated titanium dioxide;
2) get the raw materials ready: according to n-hexane: anion surfactant: acrylic acid mass ratio is that 100:18:13 chooses n-hexane, anion surfactant and acrylic acid, according to above-mentioned through silane coupler modified hydrated titanium dioxide: persimmon tannin solution: ammonium persulfate: N-N methylene-bisacrylamide: acrylic acid mass ratio is that 4:46:0.26:0.07:100 chooses through silane coupler modified hydrated titanium dioxide, persimmon tannin solution, ammonium persulfate and N-N methylene-bisacrylamide;
3) the mixed liquor preparation that contains PAA: preparation sodium hydroxide solution, in ice-water bath, described sodium hydroxide solution is joined in acrylic acid, stir, make acrylic acid degree of neutralization remain on 70%, add again N, N '-methylene-bisacrylamide, ammonium persulfate and persimmon tannin solution, constantly stir it mixed, and obtains the mixed liquor that contains PAA;
4) synthetic: by n-hexane, anion surfactant with add in reactor through silane coupler modified hydrated titanium dioxide, react 10 minutes passing under nitrogen and stirring (450 revs/min) condition, then add the resulting mixed liquor of step (3), stir, be warmed up to 75 ° of C and stir (450 revs/min) reaction 1.5h;
5) material step 4) being obtained is poured out, and filters n-hexane, and vacuum drying obtains hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent.
The solution that is 240mg/L containing plumbum ion concentration by 100ml packs in boiling flask, and the pH of solution is adjusted to 5.0, then adds the compound adsorbent of 0.1000g embodiment 1 gained, will act on liquid as for stirring in 20 ℃ of lower magnetic forces on magnetic stirring apparatus, effect 7h.Then get supernatant, with ultraviolet-uisible spectrophotometer, record concentration of metal ions in supernatant.According to n=(C
0-C
e)/C
0* 100% and q=(C
0-C
e) V/M calculates respectively adsorption rate n and adsorbance q.Wherein, C
0initial concentration (mg/L) for metal ion in the aqueous solution; C
eequilibrium concentration (mg/L) for metal ion in the aqueous solution; V is liquor capacity (L); M is compound adsorbent weight (g).The method of adsorption rate and adsorbance of calculating in following examples is all with reference to the method.
This compound adsorbent is to pb
2+adsorption rate reach 94.60%, adsorbance is 227.04mg/g, advantages of good adsorption effect.
Embodiment 2:
A preparation method for hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent, it comprises the following steps:
1) surface treatment of hydrated titanium dioxide: by hydrated titanium dioxide: the mass ratio of silane coupler is that 1:0.3 chooses silane coupler and hydrated titanium dioxide is standby, silane coupler is added to stirring and dissolving in water, then add hydrated titanium dioxide stirring reaction 12h, centrifugal (3500r/min, 20min), washing, 80 ℃ of vacuum drying, obtain through silane coupler modified hydrated titanium dioxide;
2) get the raw materials ready: according to n-hexane: anion surfactant: acrylic acid mass ratio is that 150:27:30 chooses n-hexane, anion surfactant and acrylic acid, according to above-mentioned through silane coupler modified hydrated titanium dioxide: persimmon tannin solution: ammonium persulfate: N-N methylene-bisacrylamide: acrylic acid mass ratio is that 8:46:0.26:0.07:100 chooses through silane coupler modified hydrated titanium dioxide, persimmon tannin solution, ammonium persulfate and N-N methylene-bisacrylamide;
3) the mixed liquor preparation that contains PAA: preparation sodium hydroxide solution, in ice-water bath, described sodium hydroxide solution is joined in acrylic acid, stir, make acrylic acid degree of neutralization remain on 70%, add again N, N '-methylene-bisacrylamide, ammonium persulfate and persimmon tannin solution, constantly stir it mixed, and obtains the mixed liquor that contains PAA;
4) synthetic: by n-hexane, anion surfactant with add in reactor through silane coupler modified hydrated titanium dioxide, react 15 minutes passing under nitrogen and stirring (450 revs/min) condition, then add the resulting mixed liquor of step (3), stir, be warmed up to 75 ° of C and stir (450 revs/min) reaction 1.5h;
5) material step 4) being obtained is poured out, and filters n-hexane, and vacuum drying obtains hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent.
This compound adsorbent is to pb
2+adsorption rate reach 96.47%, adsorbance is 231.52mg/g, advantages of good adsorption effect.
Embodiment 3:
A preparation method for hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent, it comprises the following steps:
1) surface treatment of hydrated titanium dioxide: by hydrated titanium dioxide: the mass ratio of silane coupler is that 1:2.4 chooses silane coupler and hydrated titanium dioxide is standby, silane coupler is added to stirring and dissolving in water, then add hydrated titanium dioxide stirring reaction 12h, centrifugal (3500r/min, 20min), washing, 80 ℃ of vacuum drying, obtain through silane coupler modified hydrated titanium dioxide;
2) get the raw materials ready: according to n-hexane: anion surfactant: acrylic acid mass ratio is that 200:36:50 chooses n-hexane, anion surfactant and acrylic acid, according to above-mentioned through silane coupler modified hydrated titanium dioxide: persimmon tannin solution: ammonium persulfate: N-N methylene-bisacrylamide: acrylic acid mass ratio is that 12:46:0.26:0.07:100 chooses through silane coupler modified hydrated titanium dioxide, persimmon tannin solution, ammonium persulfate and N-N methylene-bisacrylamide;
3) the mixed liquor preparation that contains PAA: preparation sodium hydroxide solution, in ice-water bath, described sodium hydroxide solution is joined in acrylic acid, stir, make acrylic acid degree of neutralization remain on 70%, add again N, N '-methylene-bisacrylamide, ammonium persulfate and persimmon tannin solution, constantly stir it mixed, and obtains the mixed liquor that contains PAA;
4) synthetic: by n-hexane, anion surfactant with add in reactor through silane coupler modified hydrated titanium dioxide, react 20 minutes passing under nitrogen and stirring (450 revs/min) condition, then add the resulting mixed liquor of step (3), stir (450 revs/min), be warmed up to 75 ° of C stirring reaction 1.5h;
5) material step 4) being obtained is poured out, and filters n-hexane, and vacuum drying obtains hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent.
This compound adsorbent is to pb
2+adsorption rate reach 92.02%, adsorbance is 220.84mg/g, advantages of good adsorption effect.
Above in all embodiment, silane coupler is selected γ-methacryloxypropyl trimethoxy silane, and anion surfactant is selected polyoxyethylene alkyl ether sulfate salt, as polyoxyethylene alkyl ether sulfate sodium, be understandable that, it is selected that it is not limited to above embodiment.
Above in all embodiment, the preparation method of described persimmon tannin solution comprises the steps: after the blue or green persimmon fragmentation of plucking, in blue or green persimmon: the ratio of mass ratio=1:0.5～10 of distilled water was soaked after two weeks, press again juice, filtrate is after vacuum filtration, spontaneous fermentation 1～2 year, obtains bronzing persimmon tannin solution.
Each raw material that the present invention is cited, and the bound value of each raw material, with and interval value, can realize the present invention; And the bound value of each technological parameter (as temperature, time etc.), with and interval value, can realize the present invention, at this, do not enumerate embodiment.
Claims (9)
1. a preparation method for hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent, is characterized in that it comprises the following steps:
1) surface treatment of hydrated titanium dioxide: by hydrated titanium dioxide: the mass ratio of silane coupler is that 1:0.15-2.4 chooses silane coupler and hydrated titanium dioxide is standby, silane coupler is added to stirring and dissolving in water, then add centrifugal after hydrated titanium dioxide stirring reaction 12h, washing, dry, obtain through silane coupler modified hydrated titanium dioxide, described silane coupler is γ-methacryloxypropyl trimethoxy silane;
2) get the raw materials ready: according to n-hexane: anion surfactant: acrylic acid mass ratio is that 100-200:18-36:13-50 chooses n-hexane, anion surfactant and acrylic acid, according to above-mentioned through silane coupler modified hydrated titanium dioxide: persimmon tannin solution: ammonium persulfate: N, N'-methylene-bisacrylamide: acrylic acid mass ratio is that 4-12:46:0.26:0.07:100 chooses through silane coupler modified hydrated titanium dioxide, persimmon tannin solution, ammonium persulfate and N, and N'-methylene-bisacrylamide is standby;
3) the mixed liquor preparation that contains PAA: preparation sodium hydroxide solution, in ice-water bath, described sodium hydroxide solution is joined in acrylic acid, stir, make acrylic acid degree of neutralization remain on 70%, add again N, N'-methylene-bisacrylamide, ammonium persulfate and persimmon tannin solution, constantly stir it mixed, and obtains the mixed liquor that contains PAA;
4) synthetic: by n-hexane, anion surfactant with add in reactor through silane coupler modified hydrated titanium dioxide, react 10～20 minutes passing under nitrogen and stirring condition, then add the resulting mixed liquor of step (3), stir, be warmed up to 75 ℃ of stirring reaction 1.5h;
5) material step 4) being obtained is poured out, and filters n-hexane, and vacuum drying obtains hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent.
2. preparation method as claimed in claim 1, is characterized in that, the hydrated titanium dioxide in described step 1): the mass ratio of silane coupler is 1:0.3.
3. preparation method as claimed in claim 1, is characterized in that, the centrifugation rate in described step 1) is 3500r/min, and centrifugation time is 20min.
4. preparation method as claimed in claim 1, is characterized in that, the baking temperature in described step 1) is 80 ℃, dry under vacuum condition.
5. preparation method as claimed in claim 1, is characterized in that, the stir speed (S.S.) in described step 4) is 450 revs/min.
6. preparation method as claimed in claim 1, it is characterized in that, the preparation method of described persimmon tannin solution comprises the steps: after the blue or green persimmon fragmentation of plucking, in blue or green persimmon: the ratio of mass ratio=1:0.5～10 of distilled water was soaked after two weeks, press again juice, filtrate is after vacuum filtration, and spontaneous fermentation 1～2 year, obtains bronzing persimmon tannin solution.
7. preparation method as claimed in claim 1, is characterized in that, described anion surfactant is polyoxyethylene alkyl ether sulfate salt.
8. hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent that preparation method as claimed in claim 1 makes.
9. the application of hydrated titanium dioxide-persimmon tannin acrylic resin compound adsorbent that a preparation method as claimed in claim 1 makes in lead waste water is processed.
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