CN110559990A - Preparation method of pure water carbon composite material with low nano zero-valent iron and nano silver loading - Google Patents
Preparation method of pure water carbon composite material with low nano zero-valent iron and nano silver loading Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 151
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000011068 loading method Methods 0.000 title claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 239000003651 drinking water Substances 0.000 claims abstract description 10
- 235000020188 drinking water Nutrition 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- 239000012279 sodium borohydride Substances 0.000 claims description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 34
- 229910052709 silver Inorganic materials 0.000 abstract description 20
- 239000004332 silver Substances 0.000 abstract description 15
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 238000000746 purification Methods 0.000 description 19
- 230000002829 reductive effect Effects 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 10
- 241000588724 Escherichia coli Species 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 229910001448 ferrous ion Inorganic materials 0.000 description 6
- 230000003385 bacteriostatic effect Effects 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000000120 microwave digestion Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- 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
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention relates to a preparation method of a low-nano zero-valent iron and nano silver loaded pure water carbon composite material, the low-nano zero-valent iron and nano silver loaded pure water carbon composite material prepared by the preparation method has high specific surface area, the iron loading and silver loading in the composite material are low, the particle diameters of nano zero-valent iron and nano silver are both less than 20nm, the pure water carbon composite material can simultaneously adsorb and convert or degrade various pollutants in drinking water, the release amount of iron and silver is extremely low, and the composite material is a pure water material with great application value.
Description
Technical Field
The invention relates to the field of water purification materials, in particular to a preparation method of a water purification carbon composite material with low nano zero-valent iron and nano silver loading capacity.
Background
Purified water carbon is widely used as one of the important filter core materials for terminal water purification. Due to the huge specific surface area and surface chemistry and biocompatibility, the adsorbent has an adsorption removal effect on various pollutants in water. But at the same time, the problems that microbial films are easy to grow on the surfaces of the materials and secondary pollution is caused after chemical pollutants are saturated are found, so that the using effect and safety of the materials are seriously limited. Moreover, the regeneration of the purified water carbon after adsorbing the pollutants is difficult and costly, thereby limiting the regeneration thereof and increasing the cost of the filter element material.
The load modification of the purified water carbon is one of effective ways to solve the problems. The nano zero-valent iron is a novel water purification material, and has large specific surface area, high surface reaction activity and nano core-shell structure, so that the nano zero-valent iron has the capability of converting or degrading pollutants in water in a broad spectrum. The conversion or degradation efficiency and the degradation capability of the water purification carbon loaded with the nano zero-valent iron to pollutants in water are improved. Patent publication No. CN104014812B discloses a method for preparing a composite material of activated carbon loaded with nano zero-valent iron. The performance of the activated carbon loaded with the nano zero-valent iron is improved, but the composite material can not inhibit bacteria and can not meet the requirement of inhibiting the growth of microorganisms on the surface of the activated carbon.
the nano silver has broad-spectrum bactericidal ability. Patents with publication numbers CN103232035B and CN102381704B disclose methods for preparing activated carbon-supported nano silver. Both patents have in common that the preparation is done on the basis of activated carbon impregnated with silver nitrate; the difference is that the former uses reducing agents such as sodium borohydride or D-glucose to reduce silver ions into nano silver particles in situ, and the latter heats the nano silver particles for 4-5 hours at a high temperature of 400-500 ℃ to load the nano silver on the activated carbon. Both of these methods, whether using reducing agents or conditions for preparation at high temperatures, increase the cost of the preparation.
The modification of the purified water carbon by combining the nano zero-valent iron and the nano silver can not only fundamentally solve the problems of pollutants, but also inhibit the growth of microorganisms on the surface of the purified water carbon. The nano silver is reduced on the surface of the nano zero-valent iron in situ, so that the cost of the nano silver reducing agent is reduced. The preparation of the composite material of pure water carbon loaded with nano zero-valent iron and nano silver is disclosed in patent application number CN201710211337.0, but the composite material in the patent has a low specific surface area, a large theoretical addition amount of iron, and a large particle size of the loaded nano zero-valent iron and nano silver particles, which all make the prepared composite material have low removal efficiency on lead ions and cadmium ions.
Disclosure of Invention
The invention aims to provide a preparation method of a water purification carbon composite material with low nano zero-valent iron and nano silver loading capacity, and aims to solve the problem that the existing water purification carbon has low removal efficiency of lead ions and cadmium ions.
The specific scheme is as follows:
A preparation method of a pure water carbon composite material with low nano zero-valent iron and nano silver loading comprises the following steps:
S1, washing the activated carbon, and drying for later use;
S2, adding ferrous sulfate into a mixed solvent consisting of polyethylene glycol, absolute ethyl alcohol and water, wherein the molecular weight of the polyethylene glycol is not more than 200;
S3, adding the cleaned activated carbon obtained in the step S1 into the mixed solution obtained in the step S2, stirring, adding a sodium borohydride solution, and reacting to obtain activated carbon loaded with nano zero-valent iron, wherein the mass ratio of iron elements in ferrous sulfate to the activated carbon is 1: 100-1: 200;
S4, washing the activated carbon loaded with the nano zero-valent iron prepared in the step S3, then adding the activated carbon into a silver salt solution under the protection of nitrogen, stirring uniformly, and reacting to obtain the activated carbon loaded with the nano zero-valent iron and silver metal cluster composite material.
Further, in the step S3, the dropping speed of the added sodium borohydride solution is not more than 0.28 mL/min;
Optionally, the rotation speed of stirring in the step S3 is 400-700 r/min.
Further, in the step S3, the dropping speed of the added sodium borohydride solution is 0.28mL/min to 0.15 mL/min.
Further, it is characterized byIn the step S3, the sodium borohydride solution is added in an amount of n in a molar ratioFe2+/nBH4-＝1:8～1:10。
Further, in the step S1, the drying temperature is 105 ℃, and the drying time is 48 hours.
Further, in the step S2, the volume ratio of the absolute ethyl alcohol to the water is 8: 2-9: 1.
Further, in the step S4, the concentration of the silver salt solution is C(Ag+)＝2.0～6.0mmol/L；
Optionally, the rotation speed of stirring in the step S4 is 500-700 r/min.
The invention also provides a pure water carbon composite material with low nano zero-valent iron and nano silver loading, which is prepared by the preparation method.
The invention also provides application of the low-nano zero-valent iron and nano silver loaded water purification carbon composite material prepared by the preparation method, which is used for deeply purifying terminal drinking water, removing low-concentration organic pollutants in the drinking water and inhibiting bacteria.
The preparation method of the invention takes the specific surface area of the pure water carbon as a starting point, reduces the grain diameter of nano particles and the surface oxidation degree of the nano zero-valent iron, and adopts the following conditions:
(1) The molecular weight of polyethylene glycol is reduced to 200 or below, and the molecular weight of polyethylene glycol is reduced, so that the ferrous ion precursor is reduced in spatial size, the ferrous ion precursor can easily enter a pore channel structure of the water purification carbon, the degree of blockage of the pore channel structure of micropores is reduced, and the integral specific surface area value of the composite material is increased, thereby being more beneficial to coordinating the adsorption effect of the water purification carbon and the reaction performance of the nano material;
(2) the mass ratio of the ferrous ions to the activated carbon is 1: 100-1: 200, and the using amount of the water purifying carbon in the dipping process is increased to increase the dipping amount, so that the effective utilization rate of a ferrous ion precursor is increased;
And preferred conditions:
(3) The molar ratio of sodium borohydride to ferrous ions is increased to 1: 8-1: 10, the growth time of the loaded nano zero-valent iron is obviously prolonged by increasing the molar ratio of sodium borohydride to ferrous ions, the particle size of the loaded nano zero-valent iron is greatly reduced, the surface reactivity of the loaded nano zero-valent iron is increased, and the reaction performance is improved;
(4) The dropping speed of the sodium borohydride solution is controlled to be 0.28-0.15 mL/min, and by obviously reducing the dropping speed of the sodium borohydride solution, the nucleation and growth time of the loaded nano zero-valent iron is prolonged, so that favorable conditions are provided for the complete small particle growth;
Compared with the prior art, the water purification carbon composite material prepared by the conditions has the following advantages:
1. the water purification carbon composite material prepared by the preparation method has high specific surface area, and the specific surface area of the water purification carbon composite material is reduced by less than 10% relative to that of active carbon (the specific surface area of the water purification carbon composite material in the prior art is reduced by about 70%), so that the synergistic effect between the adsorption capacity of the water purification carbon and the high reaction activity of the nano metal clusters can be better realized.
2. The particle size of the nano zero-valent iron and the nano silver in the water purification carbon composite material prepared by the preparation method is less than 20nm (the particle size of the nano zero-valent iron and the nano silver in the prior art is 50-100 nm), and the particle size is obviously reduced, so that the surface zero-valent iron atoms are increased, the surface energy is improved, and the reaction rate with pollutant molecules is accelerated.
3. The water purification carbon composite material prepared by the preparation method disclosed by the invention has the advantages that the iron loading capacity is lower than 1%, and the silver loading capacity is lower than 0.5%, so that the loss risk of the loaded nano zero-valent iron and the nano silver after reaction with water can be reduced, the preparation cost of the whole material can be reduced, and the environmental and economic benefits are improved.
4. Under the same condition, the water purification carbon composite material prepared by the preparation method has the performance of removing low-concentration lead ions and cadmium ions more efficiently.
Drawings
FIG. 1 is a graph showing the specific surface area of the composite material prepared in example 1 measured by the BET six-point method.
Fig. 2 is an XRD pattern of the composite material prepared in example 1.
fig. 3 is an SEM image of the composite material prepared in example 1.
Fig. 4 is a TEM image of the composite material prepared in example 1.
Fig. 5 is a graph of specific surface area of the composite material prepared in example 2 measured by the BET six-point method.
Fig. 6 is an XRD pattern of the composite material prepared in example 2.
Fig. 7 is an SEM image of the composite material prepared in example 2.
Fig. 8 is a TEM image of the composite material prepared in example 2.
fig. 9 shows the actual contents of iron and silver of the composite materials of examples 1 and 2, as measured by microwave digestion.
FIG. 10 shows Pb as a result of the composite and raw activated carbon obtained in examples 1 and 22+The removal efficiency of (a) is compared with that of (b).
FIG. 11 shows Cd pairs of composite and raw activated carbon prepared in examples 1 and 22+The removal efficiency of (a) is compared with that of (b).
FIG. 12 shows Pb adsorption of the composite materials obtained in examples 1 and 22+the loss analysis chart of Fe and Ag is shown later.
FIG. 13 shows Cd adsorption by the composite materials obtained in examples 1 and 22+The loss analysis chart of Fe and Ag is shown later.
FIG. 14 shows the bacteriostatic effect of the composite material prepared in example 1 on Escherichia coli.
FIG. 15 is a graph showing the effect of the composite material prepared in example 1 on the growth of E.coli.
Detailed Description
the technical solution of the present invention is further illustrated by the following examples. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by manufacturers, and are conventional products which can be directly purchased from the market.
the invention will now be further described with reference to the accompanying drawings and detailed description.
Example 1
The embodiment provides a preparation method of a pure water carbon composite material with low nano zero-valent iron and nano silver loading capacity, which comprises the following steps:
S1, screening activated carbon particles with the particle size of 1.0-1.5 mm, cleaning the activated carbon particles with deionized water, and drying the activated carbon particles for later use.
S2, according to the mass ratio of the iron element to the activated carbon of 1:100 weigh FeSO4·7H2O, adding 100mL of mixed solvent of ultrapure water and absolute ethyl alcohol with the volume ratio of 8:2 and 0.1g of polyethylene glycol-200, stirring at the rotating speed of 400r/min at room temperature, and introducing N2and the reaction time is 120min, thus preparing a mixed solution. Polyethylene glycol-200 as used herein refers to polyethylene glycol having a molecular weight of no greater than 200.
S3, adding 20g of the washed activated carbon particles into the mixed solution prepared in the step S2, and stirring for 120 min.
S4, adding 100mL of 0.29mol/L sodium borohydride solution at a dropping speed of less than 0.28mL/min, continuously stirring for 30min after the reaction is finished, and washing the activated carbon-loaded nano zero-valent iron solid particles obtained after the reaction in a flask for 3 times.
S5, mixing 100mL of AgNO with the concentration of 5.0mmol/L3Adding the solution into the activated carbon loaded nano zero-valent iron solid particles prepared in the step S4, and reacting for 30min, wherein the rotating speed of the stirrer is 500 rpm.
S6, performing suction filtration on the product obtained in the step S5, separating to obtain solid particles, namely the pure water carbon composite material loaded with the low-nanometer zero-valent iron and the nanometer silver, washing the solid particles for 3 times by using ultrapure water, performing vacuum drying at the constant temperature of 70 ℃ and under the pressure of 0.06MPa, and storing the dried solid particles in a vacuum dryer.
As shown in FIG. 1, FIG. 1 shows that the specific surface area of the pure water carbon composite material loaded with low nano zero-valent iron and nano silver prepared in the embodiment is 974m measured by a BET six-point method2(ii)/g, specific surface area to original activated carbon (997 m)2The reduction in/g) is only 2%.
as shown in fig. 9, the iron content and the silver content of the composite material prepared in this example were measured to be 0.926% and 0.015% respectively by microwave digestion.
as shown in fig. 2, fig. 2 is an XRD pattern of the composite material prepared in this example, and the composite material prepared in this example is composed of amorphous carbon, nano zero-valent iron and crystalline nano elemental silver.
As shown in fig. 3, fig. 3 is an SEM image of the composite material prepared in this embodiment, in the composite material prepared in this embodiment, the nano zero-valent iron and the nano silver are uniformly dispersed in the activated carbon, the nano zero-valent iron exists in a chain form, the nano silver exists in a form of small spherical particles, and the particle size of most of the nano zero-valent iron and the nano silver is between 10 nm and 20 nm.
As shown in FIG. 4, FIG. 4 is a TEM image of the composite material prepared in this example, in which the nanoscale zero-valent iron and the nanoscale silver are stacked together, and the particle size is 10-20 nm.
Example 2
The embodiment provides a preparation method of a pure water carbon composite material with low nano zero-valent iron and nano silver loading capacity, which comprises the following steps:
S1, screening activated carbon particles with the particle size of 1.0-1.5 mm, cleaning the activated carbon particles with deionized water, and drying the activated carbon particles for later use.
S2, weighing FeSO according to the mass ratio of the iron element to the active carbon of 1:2004·7H2O, adding 100mL of mixed solvent of ultrapure water and absolute ethyl alcohol with the volume ratio of 8:2 and 0.1g of polyethylene glycol-200, stirring at the rotating speed of 400r/min at room temperature, and introducing N2And the reaction time is 120min to prepare a mixed solution. Polyethylene glycol-200 as used herein refers to polyethylene glycol having a molecular weight of no greater than 200.
S3, adding 40g of the cleaned activated carbon particles into the mixed solution prepared in the step S2, and stirring for 120 min.
S4, adding 100mL of 0.29mol/L sodium borohydride solution at a dropping speed of less than 0.28mL/min, continuously stirring for 30min after the reaction is finished, and washing the activated carbon-loaded nano zero-valent iron solid particles obtained after the reaction in a flask for 3 times.
S5, 100mL of AgNO with the concentration of 6.0mmol/L3Adding the solution into active carbon loaded nano zero-valent iron solid particles, reacting for 30min, wherein the rotating speed of a stirrer is 500 rpm.
S6, performing suction filtration on the product obtained in the step S5, separating to obtain solid particles, namely the pure water carbon composite material loaded with the low-nanometer zero-valent iron and the nanometer silver, washing the solid particles for 3 times by using ultrapure water, performing vacuum drying at the constant temperature of 70 ℃ and under the pressure of 0.06MPa, and storing the dried solid particles in a vacuum dryer.
As shown in FIG. 5, FIG. 5 shows that the specific surface area of the pure water carbon composite material loaded with low nano-zero-valent iron and nano-silver prepared in the example is 971m by adopting a BET six-point method2(ii)/g, specific surface area to original activated carbon (997 m)2The reduction in/g) is only 2%.
As shown in fig. 9, the iron content and the silver content of the composite material prepared in this example were measured to be 0.458% and 0.019%, respectively, by a microwave digestion method.
As shown in fig. 6, fig. 6 is an XRD pattern of the composite material prepared in this example, and the composite material prepared in this example is composed of amorphous carbon, nano zero-valent iron and crystalline nano elemental silver.
As shown in fig. 7, fig. 7 is an SEM image of the composite material prepared in this embodiment, in the composite material prepared in this embodiment, the nano zero-valent iron and the nano silver are uniformly dispersed in the activated carbon, the nano zero-valent iron exists in a chain form, the nano silver exists in a form of small spherical particles, and the particle size of most of the nano zero-valent iron and the nano silver is between 10 nm and 20 nm.
As shown in FIG. 8, FIG. 8 is a TEM image of the composite material prepared in this example, in which the nanoscale zero-valent iron and the nanoscale silver are stacked together, and the particle size is 10-20 nm.
Example 3
The present example is a research experiment on the application of the water purifying carbon composite material with low nano-zero-valent iron and nano-silver loading, and mainly uses low-concentration Pb in drinking water2+and Cd2+For the subject, the samples were investigated in a constant temperature shaker by means of a static adsorption testThe adsorption performance of the composite material. The experimental conditions are C0100ppb, 1.0g/L of composite material, pH 6.0 and ionic strength CNaNO3＝0.01M。
As shown in fig. 10 and 11, wherein fig. 10 shows Pb for the composite material and the raw activated carbon prepared in examples 1 and 22+FIG. 11 is a graph showing Cd pairs of the composite and raw activated carbon prepared in example 1 and example 22 +The removal efficiency of (a) is compared with that of (b). As can be seen from FIGS. 10 and 11, the activated carbon (coconut shell activated carbon) without the nano zero-valent iron and silver metal cluster supported has the same Pb content within 10 minutes2+Basically has no adsorption and can be used for Cd2+The adsorption amount of the composite material is very small (less than 5%), and the composite material prepared by the invention can remove more than 80% of Pb in 10 minutes under the above conditions2+And about 80% of Cd2+And the removal efficiency is further improved along with the prolonging of the time, and the removal efficiency is higher than that of the blank control activated carbon material. After 30 minutes, the reaction can reach Pb basically2+100% absorption rate of and on Cd2+Near 90% absorption. After 60 minutes, the Pb can be substantially completely removed2+And Cd2+Pb relative to coconut shell activated carbon alone2+And Cd2+The degradation efficiency is obviously improved in the aspect of the adsorption effect.
As shown in FIGS. 12 and 13, FIG. 12 shows Pb adsorption of the composite materials obtained in examples 1 and 22+FIG. 13 is a graph showing the loss analysis of Fe and Ag, and the Cd absorption of the composite materials obtained in examples 1 and 22+The loss analysis chart of Fe and Ag is shown later. The above-mentioned graphs for the loss of Fe and Ag are the data measured after 1440 minutes under the conditions of this example.
As can be seen from the concentration data of iron and silver in the solution after adsorption in FIGS. 12 and 13, the maximum elution amount of iron is extremely low, and the elution amount of silver does not exceed 5 mug/L, which indicates that the material is efficient and safe in advanced treatment of drinking water.
It should be noted that this example uses Pb2+and Cd2+The subject of the present invention is not limited to the above-mentioned examples, but the present invention is applicable to various fieldsThe prepared composite material of the activated carbon loaded with the nano zero-valent iron and the silver metal cluster can also be applied to treatment of carbon tetrachloride and high-oxidizing pollutants, has an effective effect on removing various pollutants in drinking water, including residual chlorine, disinfection byproducts, soluble heavy metal ions, trace emerging pollutants, bacteria and the like, and is particularly suitable for deeply purifying the drinking water.
Example 4
In the embodiment, common escherichia coli in drinking water is mainly taken as a research object, and the bacteriostatic and sterilizing capabilities of nAg/NZVI/AC (nano zero-valent iron and silver metal cluster-loaded composite material) on e.coli (escherichia coli) are discussed by comparing the bacteriostatic and sterilizing performances of AC (activated carbon) and nAg/NZVI/AC (nano zero-valent iron and silver metal cluster-loaded composite material) on the water purifying carbon composite material with low nano zero-valent iron and nano silver loading capacity.
coli was cultured in LB (Luria-Bertani) liquid medium at 37 ℃ for 12 hours. The concentration of the culture broth was diluted to 107(CFU)/mL. 0.30g of AC and nAg/NZVI/AC were added to each of the diluted cells, and the cells were cultured at 37 ℃ for 4 hours. After the cultivation, the treated bacterial suspension is diluted 104And culturing for 12h at 37 ℃ on a solid LB culture medium. Coli was calculated by means of several dots, all experimental groups had three replicates and the colony count was the average of the three replicates.
Referring to fig. 14 and 15, fig. 14 is a graph showing the bacteriostatic effect of the sample prepared in example 1 on escherichia coli, and fig. 15 is a graph showing the bacteriostatic effect of the sample prepared in example 1 on escherichia coli. As can be seen from the figure, the pure water carbon composite material loaded with the nano zero-valent iron and the nano silver can kill all escherichia coli, and the original pure water carbon has no killing effect on the escherichia coli. This shows that the nano zero-valent iron and nano silver loaded water purification carbon composite material has excellent sterilization capability.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a pure water carbon composite material with low nano zero-valent iron and nano silver loading capacity is characterized by comprising the following steps:
S1, washing the activated carbon, and drying for later use;
S2, adding ferrous sulfate into a mixed solvent consisting of polyethylene glycol, absolute ethyl alcohol and water, wherein the molecular weight of the polyethylene glycol is not more than 200;
S3, adding the cleaned activated carbon obtained in the step S1 into the mixed solution obtained in the step S2, stirring, adding a sodium borohydride solution, and reacting to obtain activated carbon loaded with nano zero-valent iron, wherein the mass ratio of iron elements in ferrous sulfate to the activated carbon is 1: 100-1: 200;
S4, washing the activated carbon loaded with the nano zero-valent iron prepared in the step S3, then adding the activated carbon into a silver salt solution under the protection of nitrogen, stirring uniformly, and reacting to obtain the activated carbon loaded with the nano zero-valent iron and silver metal cluster composite material.
2. the method of claim 1, wherein: in the step S3, the dropping speed of the added sodium borohydride solution is not more than 0.28 mL/min;
Optionally, the rotation speed of stirring in the step S3 is 400-700 r/min.
3. The method of claim 2, wherein: in the step S3, the dropping speed of the added sodium borohydride solution is 0.28mL/min to 0.15 mL/min.
4. The method of claim 1, wherein: in the step S3, the sodium borohydride solution is added in an amount of n according to a molar ratioFe2+/nBH4-＝1:8～1:10。
5. The method of claim 1, wherein: in the step S1, the drying temperature is 105 ℃ and the drying time is 48 h.
6. the method of claim 1, wherein: in the step S2, the volume ratio of the absolute ethyl alcohol to the water is 8: 2-9: 1.
7. The method of claim 1, wherein: in the step S4, the concentration of the silver salt solution is C(Ag+)＝2.0～6.0mmol/L；
Optionally, the rotation speed of stirring in the step S4 is 500-700 r/min.
8. the method of claim 1, wherein: the active carbon is coconut shell active carbon.
9. the pure water carbon composite material with low nano zero-valent iron and nano silver loading, which is prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the pure water carbon composite material with low nano zero-valent iron and nano silver loading prepared by the preparation method according to any one of claims 1 to 8 is characterized in that: the method is used for deeply purifying terminal drinking water, removing low-concentration inorganic and organic pollutants in the drinking water and inhibiting bacteria at the same time.
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| PCT/CN2019/122351 WO2021042599A1 (en) | 2019-09-02 | 2019-12-02 | Method for preparing water-purifying charcoal composite material with low loading amount of nano zero-valent iron and nano silver |
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| CN111690175A (en) * | 2020-07-09 | 2020-09-22 | 镧明材料技术(上海)有限公司 | Preparation method and application of rare earth composite antibacterial agent doped with nano silver |
| CN111955478A (en) * | 2020-08-27 | 2020-11-20 | 中国科学院城市环境研究所 | Slow-release carbon-based antibacterial and antiviral composite material and preparation method and application thereof |
| CN112973633A (en) * | 2021-03-01 | 2021-06-18 | 中国科学院城市环境研究所 | Activated carbon-based material and preparation method and application thereof |
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| CN111690175A (en) * | 2020-07-09 | 2020-09-22 | 镧明材料技术(上海)有限公司 | Preparation method and application of rare earth composite antibacterial agent doped with nano silver |
| CN111955478A (en) * | 2020-08-27 | 2020-11-20 | 中国科学院城市环境研究所 | Slow-release carbon-based antibacterial and antiviral composite material and preparation method and application thereof |
| CN112973633A (en) * | 2021-03-01 | 2021-06-18 | 中国科学院城市环境研究所 | Activated carbon-based material and preparation method and application thereof |
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