A kind of sewage disposal vermiculite based material and its preparation method and applicationTechnical field
The present invention relates to technical field of sewage, specifically a kind of sewage disposal vermiculite based material and preparation method thereofAnd application.
Background technology
Water pollution caused by heavy metal ion is the severe environmental problem that the whole world faces, and chromium, cadmium and lead are to drawThe Heavy Metals ion of water pollution is played, wherein, the content of cadmium and lead is generally up to, maximum to human health risk.According to generationBoundary's Health Organization criterion, the highest content of cadmium and lead is not above 0.003 and 0.01mg/g in drinking water.Currently used for removal weightThe method of metal ion mainly includes UF membrane, and the methods of acid-base neutralization, sedimentation, but cost is higher, and periodically long and reaction is difficultIts extensive commercial application is limited with control.
Heavymetal Wastewater Treatment by Adsorption has efficient, easy and good selective.Common sorbing material is activeCharcoal, humic acid, sepiolite, polysaccharide resins etc..But the sorbing material industrially used at present is expensive, and extensive use is limitedSystem.And although vermiculite is that raw material is commonly used in sorbing material field, but itself poor processing effect, need supersonic high temperature calcining etc.It handles or the compounding side of being made is mixed with other raw materials with suction-operated with significant effect, expanded after high-temperature calcinationMake its structural instability, performance is unstable.
Invention content
The purpose of the present invention is to provide a kind of sewage disposal vermiculite based material and its preparation method and application, to solveThe problems mentioned above in the background art.
To achieve the above object, the present invention provides following technical solution：
A kind of sewage disposal vermiculite based material, includes according to the raw material of parts by weight：28-36 parts of vermiculite, propylene glycol monomethyl ether1-5 parts, 3-7 parts of polyacrylate, 15-25 parts of dimethylethanolamine, 5-12 parts of M-phthalic acid.
As further embodiment of the present invention：The sewage disposal vermiculite based material, includes according to the raw material of parts by weight：30-34 parts of vermiculite, 2-4 parts of propylene glycol monomethyl ether, 4-6 parts of polyacrylate, 18-22 parts of dimethylethanolamine, M-phthalic acid 7-10 parts.
As further embodiment of the present invention：The sewage disposal vermiculite based material, includes according to the raw material of parts by weight：32 parts of vermiculite, 3 parts of propylene glycol monomethyl ether, 5 parts of polyacrylate, 20 parts of dimethylethanolamine, 8 parts of M-phthalic acid.
A kind of preparation method of sewage disposal vermiculite based material, includes the following steps：
1) deionized water of 4-5 times of dimethylethanolamine and its quality is mixed, dimethylethanolaminesolution solution is made；By betweenThe ethyl alcohol of 6-7 times of phthalic acid and its quality mixes, and M-phthalic acid solution is made；
2) vermiculite crushed, cross 150-200 mesh sieve, then added in dimethylethanolaminesolution solution, 83- is first warming up to after sealing85 DEG C and stir process 1.4-1.5h at such a temperature, then heat to 116-120 DEG C and at such a temperature stir process 85-90min is cooled to room temperature；Then propylene glycol monomethyl ether and M-phthalic acid solution are added in, be first warming up to after sealing 68-71 DEG C andStir process 55-60min at this temperature then heats to 133-135 DEG C and at such a temperature stir process 48-53min, then150-155 DEG C and at such a temperature stir process 40-45min are warming up to, is down to room temperature, filtering removal filtrate, taking precipitate is washedWash drying；Mixture A is made；
3) mixture A with polyacrylate is mixed, stirs 1-1.2h at a temperature of 75-78 DEG C, then in 350 DEG C of temperatureThe lower calcining 3.5h of degree to obtain the final product.
As further embodiment of the present invention：Washing, drying are to be washed with water, 100 DEG C of oven dryings.
As further embodiment of the present invention：In step 2), the speed of agitator added in after dimethylethanolaminesolution solution is320r/min。
As further embodiment of the present invention：In step 2), the speed of agitator added in after M-phthalic acid solution is 250r/min。
Another object of the present invention is to provide application of the vermiculite based material in heavy metal-polluted water process.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention is handled vermiculite using dimethylethanolamine, M-phthalic acid etc., through different temperatures stir processVermiculite based material obtained, can effective Adsorption of Mercury, arsenic, nickel ion, have to heavy metal ion very strong adsorption capacity and fromSub- exchange capacity, in should being handled to heavy metal ions in wastewater, adsorption capacity is big, adsorption capacity is strong, efficient, processed waste waterReach the discharge standard of country.Properties of product of the present invention are stablized, and repeat and utilize, the secondary efficient energy used after calcining againReach the 95% of first time using effect, and performance is still very stable, suitable for industrialized production.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical solution in the embodiment of the present invention is clearly and completely described,Obviously, described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based in the present inventionEmbodiment, those of ordinary skill in the art's all other embodiments obtained without making creative work, allBelong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of sewage disposal vermiculite based material, including following raw material：Vermiculite 28kg, propylene glycolMethyl ether 1kg, polyacrylate 3kg, dimethylethanolamine 15kg, M-phthalic acid 5kg.
4 times of deionized water of dimethylethanolamine and its quality is mixed, dimethylethanolaminesolution solution is made；By isophthalic twoThe ethyl alcohol of 6 times of formic acid and its quality mixes, and M-phthalic acid solution is made.Vermiculite is crushed, crosses 150 mesh sieve, then adds in twoMethyl ethanol amine aqueous solution is first warming up to 83-85 DEG C and at such a temperature stir process 1.4h, then heats to 116 DEG C after sealingAnd stir process 85min, speed of agitator 320r/min at such a temperature.It is cooled to room temperature；Then add in propylene glycol monomethyl ether withM-phthalic acid solution is first warming up to 68 DEG C and at such a temperature stir process 55min, then heats to 133 DEG C simultaneously after sealingStir process 48min at such a temperature then heats to 150 DEG C and stir process 40min, speed of agitator is at such a temperature250r/min.Room temperature, filtering removal filtrate are down to, taking precipitate is washed with water, 100 DEG C of oven dryings；Mixture A is made.It willMixture A is mixed with polyacrylate, 1h is stirred at a temperature of 75 DEG C, then calcine 3.5h at a temperature of 350 DEG C to obtain the final product.
Embodiment 2
In the embodiment of the present invention, a kind of sewage disposal vermiculite based material, including following raw material：Vermiculite 36kg, propylene glycolMethyl ether 5kg, polyacrylate 7kg, dimethylethanolamine 25kg, M-phthalic acid 12kg.
5 times of deionized water of dimethylethanolamine and its quality is mixed, dimethylethanolaminesolution solution is made；By isophthalic twoThe ethyl alcohol of 7 times of formic acid and its quality mixes, and M-phthalic acid solution is made.Vermiculite is crushed, crosses 200 mesh sieve, then adds in twoMethyl ethanol amine aqueous solution is first warming up to 85 DEG C and at such a temperature stir process 1.5h after sealing, then heat to 120 DEG C andStir process 90min at this temperature, speed of agitator 320r/min.It is cooled to room temperature；Then propylene glycol monomethyl ether and isophthalic are added inDiformazan acid solution is first warming up to 71 DEG C and at such a temperature stir process 60min, then heats to 135 DEG C and at this after sealingAt a temperature of stir process 53min, then heat to 155 DEG C and at such a temperature stir process 45min, speed of agitator 250r/min.Room temperature, filtering removal filtrate are down to, taking precipitate is washed with water, 100 DEG C of oven dryings；Mixture A is made.It will mixingObject A is mixed with polyacrylate, 1.2h is stirred at a temperature of 78 DEG C, then calcine 3.5h at a temperature of 350 DEG C to obtain the final product.
Embodiment 3
In the embodiment of the present invention, a kind of sewage disposal vermiculite based material, including following raw material：Vermiculite 30kg, propylene glycolMethyl ether 2kg, polyacrylate 4kg, dimethylethanolamine 18kg, M-phthalic acid 7kg.
5 times of deionized water of dimethylethanolamine and its quality is mixed, dimethylethanolaminesolution solution is made；By isophthalic twoThe ethyl alcohol of 7 times of formic acid and its quality mixes, and M-phthalic acid solution is made.Vermiculite is crushed, crosses 200 mesh sieve, then adds in twoMethyl ethanol amine aqueous solution is first warming up to 84 DEG C and at such a temperature stir process 1.5h after sealing, then heat to 118 DEG C andStir process 90min at this temperature, speed of agitator 320r/min.It is cooled to room temperature；Then propylene glycol monomethyl ether and isophthalic are added inDiformazan acid solution is first warming up to 70 DEG C and at such a temperature stir process 60min, then heats to 134 DEG C and at this after sealingAt a temperature of stir process 50min, then heat to 155 DEG C and at such a temperature stir process 45min, speed of agitator 250r/min.Room temperature, filtering removal filtrate are down to, taking precipitate is washed with water, 100 DEG C of oven dryings；Mixture A is made.It will mixingObject A is mixed with polyacrylate, 1.1h is stirred at a temperature of 76 DEG C, then calcine 3.5h at a temperature of 350 DEG C to obtain the final product.
Embodiment 4
In the embodiment of the present invention, a kind of sewage disposal vermiculite based material, including following raw material：Vermiculite 34kg, propylene glycolMethyl ether 4kg, polyacrylate 6kg, dimethylethanolamine 22kg, M-phthalic acid 10kg.
5 times of deionized water of dimethylethanolamine and its quality is mixed, dimethylethanolaminesolution solution is made；By isophthalic twoThe ethyl alcohol of 7 times of formic acid and its quality mixes, and M-phthalic acid solution is made.Vermiculite is crushed, crosses 200 mesh sieve, then adds in twoMethyl ethanol amine aqueous solution is first warming up to 84 DEG C and at such a temperature stir process 1.5h after sealing, then heat to 118 DEG C andStir process 90min at this temperature, speed of agitator 320r/min.It is cooled to room temperature；Then propylene glycol monomethyl ether and isophthalic are added inDiformazan acid solution is first warming up to 70 DEG C and at such a temperature stir process 60min, then heats to 134 DEG C and at this after sealingAt a temperature of stir process 50min, then heat to 155 DEG C and at such a temperature stir process 45min, speed of agitator 250r/min.Room temperature, filtering removal filtrate are down to, taking precipitate is washed with water, 100 DEG C of oven dryings；Mixture A is made.It will mixingObject A is mixed with polyacrylate, 1.1h is stirred at a temperature of 76 DEG C, then calcine 3.5h at a temperature of 350 DEG C to obtain the final product.
Embodiment 5
In the embodiment of the present invention, a kind of sewage disposal vermiculite based material, including following raw material：Vermiculite 32kg, propylene glycolMethyl ether 3kg, polyacrylate 5kg, dimethylethanolamine 20kg, M-phthalic acid 8kg.
5 times of deionized water of dimethylethanolamine and its quality is mixed, dimethylethanolaminesolution solution is made；By isophthalic twoThe ethyl alcohol of 7 times of formic acid and its quality mixes, and M-phthalic acid solution is made.Vermiculite is crushed, crosses 200 mesh sieve, then adds in twoMethyl ethanol amine aqueous solution is first warming up to 84 DEG C and at such a temperature stir process 1.5h after sealing, then heat to 118 DEG C andStir process 90min at this temperature, speed of agitator 320r/min.It is cooled to room temperature；Then propylene glycol monomethyl ether and isophthalic are added inDiformazan acid solution is first warming up to 70 DEG C and at such a temperature stir process 60min, then heats to 134 DEG C and at this after sealingAt a temperature of stir process 50min, then heat to 155 DEG C and at such a temperature stir process 45min, speed of agitator 250r/min.Room temperature, filtering removal filtrate are down to, taking precipitate is washed with water, 100 DEG C of oven dryings；Mixture A is made.It will mixingObject A is mixed with polyacrylate, 1.1h is stirred at a temperature of 76 DEG C, then calcine 3.5h at a temperature of 350 DEG C to obtain the final product.
Comparative example 1
In addition to dimethylethanolamine is not contained, formula and preparation process are consistent with embodiment 5.
Comparative example 2
In addition to M-phthalic acid is not contained, formula and preparation process are consistent with embodiment 5.
Comparative example 3
It does not contain dimethylethanolamine and outside M-phthalic acid, formula and preparation process is consistent with embodiment 5.
Comparative example 4
Each raw material is mixed, other raw materials in embodiment is added in, 1.1h is stirred at a temperature of 76 DEG C, then at 350 DEG CAt a temperature of calcine 3.5h to obtain the final product.Its raw material component is consistent with embodiment 5.
Comparative example 5
After each raw material is mixed, 30min is ultrasonically treated, 1.1h is stirred at a temperature of 76 DEG C, then at a temperature of 350 DEG CCalcine 3.5h to obtain the final product.Its raw material component is consistent with embodiment 5.
Embodiment 6
Adsorption test of the present invention to mercurous ions mimic water：Select 5 kinds of vermiculite based materials prepared by above-described embodiment byFollowing waste water treatment process, experimental result are included in table 1.And it is compared with the product of comparative example 1-5.
(1) the simulated wastewater 1000mL that the initial concentration containing mercury ion is 550mg/L is taken；
(2) pH value is adjusted in the range of 2.0~8.5；
(3) present invention is added in into simulated water sample, vermiculite based material dosage is 1.0g/L water samples, at room temperature stirring and adsorbing20min；
(4) the static concentration for taking supernatant aas determination mercury ion calculates adsorption capacity.
Table 1
| Vermiculite based material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Adsorption capacity (mg/g) | 351.2 | 368.5 | 411.5 | 423.8 | 461.7 |
| Vermiculite based material | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Adsorption capacity (mg/g) | 108.5 | 88.4 | 35.3 | 106.8 | 115.6 |
As seen from Table 1, the present invention is 461.7mg/g to the maximum adsorption capacity of mercury ion.
Embodiment 7
Adsorption test of the present invention to the simulation water containing arsenic ion：Select 5 kinds of vermiculite based materials prepared by above-described embodiment byThe waste water treatment process of embodiment 6, the initial concentration of arsenic ion is 350mg/L, and experimental result is included in table 2.
Table 2
| Vermiculite based material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Adsorption capacity (mg/g) | 209.5 | 225.7 | 315.2 | 322.8 | 337.2 |
| Vermiculite based material | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Adsorption capacity (mg/g) | 85.2 | 122.8 | 48.2 | 90.1 | 108.2 |
As seen from Table 2, the present invention is 337.2mg/g to the maximum adsorption capacity of arsenic ion.
Embodiment 8
Adsorption test of the present invention to nickeliferous ions mimic water：Select 5 kinds of vermiculite based materials prepared by above-described embodiment byThe waste water treatment process of embodiment 6, the initial concentration of nickel ion is 280mg/L, and experimental result is included in table 3.
Table 3
| Vermiculite based material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Adsorption capacity (mg/g) | 171.6 | 202.8 | 236.8 | 246.2 | 266.1 |
| Vermiculite based material | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Adsorption capacity (mg/g) | 68.1 | 113.5 | 28.6 | 71.5 | 88.3 |
As seen from Table 3, the maximum adsorption capacity of the invention to nickel ion is 266.1mg/g.
When the content of heavy metal ion is less than the adsorption capacity of vermiculite based material in wastewater sample, adsorption rate is reachable100%, it is a kind of material of good absorption heavy metal ion.
It is obvious to a person skilled in the art that the present invention is not limited to the details of above-mentioned exemplary embodiment, Er QieIn the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matterFrom the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended powerProfit requirement rather than above description limit, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claimsVariation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrappedContaining an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art shouldIt considers the specification as a whole, the technical solutions in each embodiment can also be properly combined, forms those skilled in the artThe other embodiment being appreciated that.