CN105251446B - A kind of underground water Compound Heavy Metals repair materials - Google Patents

A kind of underground water Compound Heavy Metals repair materials Download PDF

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CN105251446B
CN105251446B CN201510764403.8A CN201510764403A CN105251446B CN 105251446 B CN105251446 B CN 105251446B CN 201510764403 A CN201510764403 A CN 201510764403A CN 105251446 B CN105251446 B CN 105251446B
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underground water
repair materials
materials
heavy metals
heavy metal
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CN105251446A (en
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郭沨
杜成琼
童纯清
涂书新
沈前
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PowerChina Zhongnan Engineering Corp Ltd
PowerChina Environmental Protection Technology Co Ltd
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Hunan Central-South Water Utilities Environmental Protection Technology Co Ltd
PowerChina Zhongnan Engineering Corp Ltd
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Abstract

The invention discloses a kind of underground water Compound Heavy Metals repair materials, by weight, including following raw material:5 17 parts of 1 part of activated carbon, 1.3 2 parts of zeolite and slag;Above-mentioned raw materials are calcined 1 5h at 150 200 DEG C after mixing, pelletizing and obtain the repair materials.The present invention is being improved heavy metal adsorption, is improving a variety of cooperative effects such as physics and chemical property, realized and the underground water of various heavy combined pollution is efficiently repaired by mixture different materials using between material;The present invention is obvious to Compound Heavy Metals fixed effect in underground water, can significantly reduce underground water content of beary metal, ensures ecological safety;The present invention is applicable different degrees of heavy metal pollution underground water, it can be allowed to contact the different time with underground water to improve removal effect according to actual conditions, and fixative cost is cheap, economically feasible.

Description

A kind of underground water Compound Heavy Metals repair materials
Technical field
The present invention relates to a kind of underground water Compound Heavy Metals repair materials, belong to underground water heavy metal pollution and repair skill Art field.
Background technology
Underground water is one of natural resources for the survival of mankind.As modern industry and agriculture develop rapidly, industry The three wastes and agricultural chemicals containing heavy metal, a large amount of apply of fertilizer cause the pollution of heavy metal in underground water turns into influence groundwater environment The principal element of quality.Heavy metal pollution and Environmental and ecological problems have seriously affected sustainable development and the mankind of economy Health, receive the extensive concern of people from all walks of life.In recent years, heavy-metal composite pollution is on the rise.In order to fundamentally prevent Heavy metal enters environment and food chain, it is necessary to heavy metal pollution in underground water is repaired, reduces the suction of biological heavy metal Receive accumulation.Underground water heavy metal pollution recovery technique mainly includes physics, chemistry and biological prosthetic three kinds, and various technologies have original again Position and dystopy point, wherein in-situ chemical reparation have the advantages that simple to operate, cost is low, time-consuming short, efficiency high and it is extensive Research.
CN201410430508 discloses a kind of Novel underground water heavy metal pollution repair materials, is 2.5- by adding pH After 3 liquor ferri trichloridi is modified to sawdust, significantly improve its absorption property to chromium, for the chromium in underground water Processing;The method that CN201310153057, CN200910272494 and CN201010203313 individually disclose removing arsenic in water, is related to And the useful sulfuric acid solution of material soak natural iron content manganese ore, rutile, titaniferous manganese material, containing Ferromanganese Ore, sharp state type nanometer two Titanium oxide 5-15kg;Activated coco nut charcoal 10-20kg, Portland cement etc..Above-mentioned patent is only to be directed to a single huge sum of money Category is removed, and actually underground water heavy metal pollution is more based on combined pollution, and therefore, above-mentioned patent cannot be used for handling The underground water of Compound Heavy Metals.
The content of the invention
Present invention solves the technical problem that being, underground water is polluted by various heavy and is difficult to once be repaired, there is provided one Kind can remove the repair materials of various heavy simultaneously, while will not introduce new impurity, not polluted underground water;Cost simultaneously It is cheap, advantages of good adsorption effect.
The technical scheme is that, there is provided a kind of underground water Compound Heavy Metals repair materials, by weight, including Following raw material:1 part of activated carbon, zeolite 1.3-2 parts and slag 5-17 parts;By above-mentioned raw materials after mixing, pelletizing at 150-200 DEG C Lower roasting 1-5h obtains the repair materials.
Further, the raw material of the repair materials also includes the bentonite no more than 2 parts and the nanometer no more than 0.5 part Titanium dioxide.
Further, the nano titanium oxide is sharp state type nano titanium oxide.
Further, the activated carbon is activated coco nut charcoal.
Further, the granularity of the activated carbon, zeolite and slag is 60-120 mesh.
Underground water Compound Heavy Metals repair materials prepared by the present invention are selected from the material of generally existing in environment, nothing Poison is harmless and cheap.According to market constant price, 1 ton of sorbing material of the invention is often prepared, about needs the cost people Coin 250-500 members.
Underground water Compound Heavy Metals fixative prepared by the present invention has good repairing effect.In theory, for compound The more serious underground water of heavy metal pollution, suitably to increase the amount of fixative;And for the lighter underground of Compound Heavy Metals Water, it is possible to reduce addition.It should be noted that in underground water Compound Heavy Metals, each heavy metal pollution degree is different, because This, for the big heavy metal of pollution level, thus it is possible to vary the sorbing material ratio used in fixative, to reach best repair effect Fruit.If heavy metal pollution is no longer influenced by by the polluted underground water repaired, and water chemistry property does not occur to change greatly, the ground Secondary pollution will not occur again for lower water.
The various materials that the present invention utilizes are common readily available material.Single material is deposited when removing removing heavy metals It is not high in removal ability, or it is only capable of removing the physicochemical properties of a kind of or a kind of heavy metal or single composite material not The shortcomings of being adapted to practical application.It is therefore desirable to which different combinations of materials is got up, while optimize proportioning and modified, utilization The synergy of different materials is so as to realizing the reparation to various heavy polluted underground water.In the sorbing material of sampling, respectively Sorbing material is had nothing in common with each other for different heavy metal adsorptions and mechanism:
Slag all has very strong absorption crystallized ability to arsenic, lead, zinc, cadmium.On the one hand iron and manganese oxides therein can be with Trivalent arsenic is oxidized to pentavalent arsenic, on the other hand, slag is with alkalescence and with large surface area, and surface site is more, to more Heavy metal species have very strong adsorption crystallized ability simultaneously, and its shortcoming is the bad unsuitable practical application of physical property.
Direct oxidation effect of the nano titanium oxide to arsenic is also very strong.Its surface charge is high, specific surface area is big, has abundant Activated adoption site, it is preferable to the adsorption effect of pentavalent arsenic.And for Cd2+、Pb2+、Zn2+Etc. heavy metal ion, it may have compared with Strong surface and Inter layer adsorption ability, and heavy metal adsorption fix material, but its shortcoming is that price is high.
The three-dimensional structure of zeolite causes it to have very big space;Secondly, Al in tetrahedron3+Substitute Si4+Office can be produced again Portion is negatively charged;Na, Ca, K etc. positively charged exchangeable ion tends to take up the space in structure, is located in zeolite in passage Cation Na and Ca etc. and Si-Al backbones to contact power weaker, can be by other cation replacements without destroying character.Therefore, pass through The zeolite for crossing processing can substitute these positively charged exchangeable ions for heavy metal cations such as cadmium, lead, copper, zinc, So as to have the function that removing heavy metals.
Montmorillonite is bentonitic main mineral constituent, the isomorph occurred in montmorillonite octahedral layer, can strengthen knot Degree of contact between structure elementary layer and be not easy to disperse, heavy metal ion possesses good exchangeability and Selective adsorption.Will After being modified in montmorillonite immersion electrolyte solution, such as Ca2+Matter montmorillonite is processed into Na+Matter montmorillonite, its inter-layer bonding force become It is small and easily scattered, expand with it is hydrophilic so that cation easily is in diffusing into interlamination region, so as to greatly improve velocity of ion exchange, Therefore sodium bentonite is to Cd2+、Pb2+、Zn2+Etc. heavy metal ion ion exchangeable and adsorbance apparently higher than in general Bentonite, but, montmorillonite is bad to the heavy mental treatment effect such as arsenic of anionic type.
Activated carbon is due to multistage, a large amount of, ordered arrangement micropores, therefore pore volume is big, aperture is big, and specific surface area is big, Absorption property is strong, can effectively adsorb Cd2+、Pb2+、Cu2+Etc. heavy metal ion.
Experiment shows that various materials have his own strong points, and makes full use of the synergy of different materials, it is possible to realizes to compound The removal of heavy metal is modified for use.Therefore, added in the underground water of Compound Heavy Metals using permeable reactive wall technology in situ Add a certain proportion of above-mentioned fixed agent material, can effectively remove each heavy metal.And fixative addition is higher, underground water is in PRB The middle residence time is longer, then stronger to the removal ability of heavy metal in underground water.
The invention has the advantages that by mixture different materials, using between material improve heavy metal adsorption, Improve a variety of cooperative effects such as physics and chemical property, realize first and height is carried out to the underground water of various heavy combined pollution Effect is repaired.Therefore, the present invention is with more actual use value;The fixative material requested of the present invention is common, and preparation process is very Simply, will be mixed with by the raw material selected;The present invention is to Compound Heavy Metals in underground water(As、Cd、Pb、Zn)Gu Determine positive effect, underground water content of beary metal can be significantly reduced, ensure ecological safety;The present invention is applicable a different degrees of huge sum of money Belong to polluted underground water, it can be allowed to contact the different time with underground water according to actual conditions to improve removal effect, and it is fixed Agent cost is cheap, economically feasible.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
The present embodiment provides a kind of underground water Compound Heavy Metals repair materials, and by weight, raw material is by 1 part of activated carbon (100 mesh), 2 parts of zeolites (80 mesh) and 17 parts of slag (100 mesh) compositions;By above-mentioned raw materials through mixing, again through extruder grain mechanism Into about 2cm spherical particles, then it is calcined 3h at 180 DEG C and obtains the repair materials.
Embodiment 2
The present embodiment provides a kind of underground water Compound Heavy Metals repair materials, and by weight, raw material is by 1 part of cocoanut shell Activated carbon (100 mesh), 1.5 parts of zeolites (100 mesh), 2 parts of bentonites (100 mesh), 0.5 part of nano titanium oxide and 5 parts of slags (80 Mesh) composition;By above-mentioned raw materials through mixing, about 1.7cm spherical particles being made through Squeezinggranulator again, then 4h is calcined at 160 DEG C Obtain the repair materials.
Embodiment 3
The present embodiment provides a kind of underground water Compound Heavy Metals repair materials, and by weight, raw material is by 1 part of cocoanut shell Activated carbon (100 mesh), 1.3 parts of zeolites (100 mesh), 1.3 parts of bentonites (100 mesh), 0.4 part of nano titanium oxide and 10 parts of slags (100 mesh) forms;By above-mentioned raw materials through mixing, about 2.5cm spherical particles being made through Squeezinggranulator again, then roasted at 200 DEG C Burn 2h and obtain the repair materials.
Embodiment 4
The repair materials that embodiment 1,2,3 is obtained respectively are used for simulated test, and step is as follows:Weigh various repair materials Sample 5.00g, it is placed in 1000mL vials, it is NaCl=40mmol/L to add 500mL background ionic strengths, As (III), Pb, Zn, Cd ion concentration are respectively 10.00 mg/L, 25mg/L, 40mg/L, 50mg/L and solution, shake 2h at 25 DEG C (The r/min of rotating speed 180), filtering, cross 0.46 μm of filter membrane.Sample liquid is taken to determine each content of beary metal.Each sample is repeated 3 times.Respectively The test data of embodiment is closer to, and underground water outlet arsenic reduces 99.8-99.9%;Cadmium reduces 99.5-99.8%;Lead reduces 99.2-99.5%;Zinc reduces 99.2-99.8%.
Embodiment 5
Certain District, Hunan gangue landfill yard underground water is taken, it is respectively 0.135 mg/ to measure As, Pb, Zn, Cd heavy metal concentration L, 0.108 mg/L, 0.401 mg/L, 0.110 mg/L, pH6.1;Tested by the test procedure of embodiment 4;Experiment knot Fruit is:Underground water outlet arsenic reduces 99.8-99.9%;Cadmium reduces 99.8-100%;Lead reduces 99.2-99.5%;Zinc reduces 99.5-100%。
Embodiment 6
Lead-zinc Deposits of Certain District, Hunan landfill yard underground water is taken, it is respectively 0.087 mg/ to measure As, Pb, Zn, Cd heavy metal concentration L, 0.708 mg/L, 1.201 mg/L, 0.140 mg/L, pH6.4.Tested by the test procedure of embodiment 4;Experiment knot Fruit is:Underground water outlet arsenic reduces 99.9%-100%;Cadmium reduces 99.7-100%;Lead reduces 99.5-99.7%;Zinc reduces 99.8-100%。

Claims (5)

  1. A kind of 1. underground water Compound Heavy Metals repair materials, it is characterised in that by weight, including following raw material:
    1 part of activated carbon, zeolite 1.3-2 parts and slag 5-17 parts;
    Above-mentioned raw materials are calcined 1-5h at 150-200 DEG C after mixing, pelletizing and obtain the repair materials.
  2. 2. repair materials as claimed in claim 1, it is characterised in that the raw material of the repair materials also includes being no more than 2 parts Bentonite and nano titanium oxide no more than 0.5 part.
  3. 3. repair materials as claimed in claim 2, it is characterised in that the nano titanium oxide is sharp state type nanometer titanium dioxide Titanium.
  4. 4. repair materials as claimed in claim 1, it is characterised in that the activated carbon is activated coco nut charcoal.
  5. 5. repair materials as claimed in claim 1, it is characterised in that the granularity of the activated carbon, zeolite and slag is 60- 120 mesh.
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CN105948165A (en) * 2016-06-23 2016-09-21 中国有色桂林矿产地质研究院有限公司 Method for regulating permeability of permeable reactive barrier (PRB)
CN109012641B (en) * 2018-08-29 2021-07-13 宝钢湛江钢铁有限公司 Preparation method of modified steel slag heavy metal adsorbent
CN111346591B (en) * 2020-03-20 2021-07-09 中国科学院过程工程研究所 Iron-based-bentonite/carbon composite porous material, and preparation method and application thereof
CN111790352B (en) * 2020-06-28 2021-11-05 中国地质大学(武汉) Adsorbent capable of removing heavy metals in industrial wastewater and preparation method thereof
CN114132984A (en) * 2021-11-10 2022-03-04 同济大学 Method for treating heavy metals in underground water

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