阅读说明：本技术 一种重金属处理用磁性纳米Fe-S材料的制备方法 (The one heavy metal species processing preparation method of magnetic Nano Fe-S material ) 是由 高卫民 程寒飞 詹茂华 于 2019-06-28 设计创作，主要内容包括：本发明公开了一种重金属处理用磁性纳米Fe-S材料的制备方法。所述的方法包括以下步骤：(1)按照比例,分别配制预定浓度同体积的亚铁盐、硫化物和氧化剂溶液；(2)将装有水的烧杯,搅拌下加热至预定温度,曝气,并加入稳定剂,溶解；(3)将步骤(1)配制的亚铁盐、硫化物和氧化剂溶液,搅拌并曝气下同时滴加到步骤(2)的水溶液中,并用碱液调节pH；(4)滴加完毕后保温,搅拌并曝气反应预定时间,期间用碱液保持pH；(5)自然冷却至室温,反应结束,过滤,水洗至中性,真空干燥制得重金属处理用磁性纳米Fe-S材料。本发明的方法具有材料安全环保、制备工艺简单,使用方便等优势,可广泛用于重金属污染土壤、废水处理系统,也可以用于存在重金属污染的河道底泥、市政污泥以及飞灰、矿山等的治理。(The invention discloses the preparation methods of a heavy metal species processing magnetic Nano Fe-S material.The method is the following steps are included: (1) proportionally, prepares ferrous salt, sulfide and the oxidizing agent solution of predetermined concentration same volume respectively；(2) beaker of water will be housed, predetermined temperature is heated under stirring, be aerated, and stabilizer is added, dissolved；(3) ferrous salt, sulfide and the oxidizing agent solution for preparing step (1), stirs and is aerated down while being added drop-wise in the aqueous solution of step (2), and adjusts pH with lye；(4) it is kept the temperature after being added dropwise, stirs the simultaneously aeration reaction predetermined time, during which keep pH with lye；(5) cooled to room temperature, reaction terminate, and filtering is washed to neutrality, are dried in vacuo and heavy metal processing magnetic Nano Fe-S material is made.Method of the invention has material safety and environmental protection, preparation process simple, the advantages such as easy to use, it can be widely used for heavy-metal contaminated soil, waste water treatment system, can be used for that there are the improvement of the river bottom mud of heavy metal pollution, municipal sludge and flying dust, mine etc..)

1. a heavy metal species processing use magnetic Nano Fe-S material preparation method, which is characterized in that the method include with Lower step:

(1) proportionally, ferrous salt, sulfide and the oxidizing agent solution of predetermined concentration same volume are prepared respectively；

(2) beaker of water will be housed, predetermined temperature is heated under stirring, be aerated, and stabilizer is added, dissolved；

(3) ferrous salt, sulfide and the oxidizing agent solution for preparing step (1), stirs and is aerated down while being added drop-wise to step (2) Aqueous solution in, and with lye adjust pH；

(4) it is kept the temperature after being added dropwise, stirs the simultaneously aeration reaction predetermined time, during which keep pH with lye；

(5) cooled to room temperature, reaction terminate, and filtering is washed to neutrality, are dried in vacuo obtained heavy metal processing and are received with magnetism Rice Fe-S material.

2. the preparation method that magnetic Nano Fe-S material is used in heavy metal species processing as described in claim 1, it is characterised in that Ferrous salt, sulfide, oxidant, stabilizer the mass ratio of the material are 1:0.5~2:A:B；Wherein, 0 < A < 0.1:0 < B < 0.01.

3. the preparation method that magnetic Nano Fe-S material is used in heavy metal species processing as described in claim 1, it is characterised in that Step (1) ferrous salt, sulfide, oxidizing agent solution concentration be 0.001~10mol/L.

4. the preparation method that magnetic Nano Fe-S material is used in heavy metal species processing as described in claim 1, it is characterised in that Step (2) predetermined temperature is room temperature~100 DEG C, and aeration quantity is 0.1~50L/min.

5. the preparation method that magnetic Nano Fe-S material is used in heavy metal species processing as described in claim 1, it is characterised in that The ferrous salt, sulfide and oxidizing agent solution rate of addition of step (3) same volume are 0.001~1L/min.

6. the preparation method that magnetic Nano Fe-S material is used in heavy metal species processing as described in claim 1, it is characterised in that Step (3) pH is 8~12.

7. the preparation method that magnetic Nano Fe-S material is used in heavy metal species processing as described in claim 1, it is characterised in that It is room temperature~100 DEG C that the insulation reaction of step (4), which stops temperature, and the reaction predetermined time is 1~10h.

8. heavy metal species processing magnetic Nano Fe-S material as described in claim 1 and preparation method thereof, feature exists In sulfide be vulcanized sodium, potassium sulfide, sodium bisulfide, one or more kinds of mixtures in potassium hydrogen sulfide.

9. heavy metal species processing magnetic Nano Fe-S material as described in claim 1 and preparation method thereof, feature exists In oxidant be hydrogen peroxide, sodium peroxide, potassium peroxide, calper calcium peroxide, peromag, barium peroxide, sodium hypochlorite, sulfurous Sour sodium, sodium hydrogensulfite, potassium sulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, sodium peroxydisulfate, hydrogen persulfate It is sodium, potassium peroxydisulfate, potassium hydrogen persulfate, ammonium persulfate, SODIUM PERCARBONATE, potassium percarbonate, sodium perborate, a kind of in potassium perborate or two Kind or more mixture.

10. heavy metal species processing magnetic Nano Fe-S material as described in claim 1 and preparation method thereof, feature exists In stabilizer be alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, polyoxyethylene carboxylate, polyoxyethylene amine, One or more kinds of mixtures in Pluronic F68, polyvinyl alcohol.

Technical field

The invention belongs to field of environmental improvement, are related to the preparation side of a heavy metal species processing magnetic Nano Fe-S material Method.

Background technique

Heavy Metals In Environment refers generally to copper (Cu), lead (Pb), zinc (Zn), chromium (Cr), nickel (Ni), mercury (Hg), cadmium (Cd) and arsenic (As).It is heavy metal-polluted to have a finger in every pie the environmental pollution as caused by heavy metal or its compound.Its extent of injury depends on weight Metal concentration present in environment, food and organism and chemical form.Heavy metal pollution is mainly found expression in water pollution, also Some is in atmosphere and solid waste.The pollution main source industrial pollution of heavy metal, followed by traffic pollution and life Refuse pollution living.Industrial pollution passes through waste residue, waste water, exhaust gas mostly and is discharged into environment, not only will affect eco-environmental quality, simultaneously Also very big harm can be caused to the health of people.

Related data statistical representation, the cultivated area that China has been contaminated have had reached 20,000,000 km², about Occupy the 20% of total area under cultivation.From agriculture level analysis, the survey showed that for the Ministry of Agriculture, and heavy industry is sent out in provinces and cities, 24, China It opens up in faster 320 emphasis area, the exceeded area of heavy metal pollution is 600,000 km², occupy 20% or more of total investigation area.Weight The agricultural output and area of overrun metal content pollute exceeded agricultural product amount in 80% or more, especially lead, cadmium, mercury, copper etc. And combined pollution performance is even more serious.Many vegetables, grain, the cadmium in fruit muddy, lead equal size exceed level threshold value, portion Region-by-region severely exceeds.Water is Source of life, and animals and plants and the mankind be unable to do without water resource, mankind's drinking water be mostly reservoir water and Underground water.From drinking water level analysis, China's city rivers pollution problem is extremely serious, about 18.46% urban river Cadmium content in pollution all has exceeded III class water body standard.By inquiry from the point of view of seven flood tying fruit of China, in nineteen ninety-five the Changjiang river In southern cadmium content in water body investigation, it is only second to mercury, COD, BOD, volatile phenol.About 16.7% there is cadmium metals in Yellow River System The exceeded situation of element.Lake, all there is the pollutions of certain cadmium metal in reservoir Statistical monitor it can be found that each basin carrying out Problem, pollution are only second to mercury pollution.

Currently, common environment heavy metal control measures have engineering measure, physical-chemical measure and biological control measure, wherein Engineering measure refers mainly to dilute heavy metal using engineering means, reduced its concentration；Physical-chemical measure passes through special material, Change Heavy Metals, makes its stabilisation；Biological control measure absorbs heavy metal by the absorption such as plant, microorganism；Analysis these types Measure cuts both ways, and wherein engineering is quick, but project amount is big, at high cost, and is not thorough；Physical-chemical measure works Fastly, project amount is moderate, but has the risk of secondary pollution, and cost is also higher；Biological control measure safety and environmental protection, cost is relatively low, But the period is long.With the development of material science, physical-chemical measure is one of research hotspot from now on, there is better application Prospect.But there is also many shortcomings for existing heavy metal processing material, such as higher cost, stability is weak, processing is single The problems such as one property.Although can with the short time quickly by heavy metal adsorption, curing/stabilizing, deposit in the environment have it is secondary The risk of release, so being badly in need of developing a kind of safety and environmental protection, the material that can rapidly and efficiently remove heavy metal from environment.

Summary of the invention

In view of the above-mentioned problems, the present invention provides the preparation method of a heavy metal species processing magnetic Nano Fe-S material, It is strong using nano magnetic material large specific surface area, adsorption capacity made from this method, and have very strong reproducibility, it can will be malicious The higher high-valence state heavy metal of property is reduced to the low lower valency of toxicity, while being adsorbed to material surface, passes through the side of Magneto separate Method is quickly removed from environment.It can be used for the Heavy-metal Polluted Environments such as soil, water body to administer and repair.

In order to achieve the above objectives, the heavy metal species processing of the invention preparation method of magnetic Nano Fe-S material, it is special Sign is,

The method the following steps are included:

(1) proportionally, ferrous salt, sulfide and the oxidizing agent solution of predetermined concentration same volume are prepared respectively；

(2) beaker of water will be housed, predetermined temperature is heated under stirring, be aerated, and stabilizer is added, dissolved；

(3) ferrous salt, sulfide and the oxidizing agent solution for preparing step (1), stirs and is aerated down while being added drop-wise to step Suddenly in the aqueous solution of (2), and pH is adjusted with lye；

(4) it is kept the temperature after being added dropwise, stirs the simultaneously aeration reaction predetermined time, during which keep pH with lye；

(5) cooled to room temperature, reaction terminate, and filtering is washed to neutrality, are dried in vacuo obtained heavy metal processing and use magnetic Property nanometer Fe-S material.

Preferably, ferrous salt, sulfide, oxidant, stabilizer the mass ratio of the material are 1:0.5~2:A:B；Wherein, 0 < A < 0.1:0 < B < 0.01.

Preferably, step (1) ferrous salt, sulfide, oxidizing agent solution concentration be 0.001~10mol/L.

Preferably, step (2) predetermined temperature is room temperature~100 DEG C, and aeration quantity is 0.1~50L/min.

Preferably, the ferrous salt, sulfide and oxidizing agent solution rate of addition of step (3) same volume are 0.001~1L/ min。

Preferably, step (3) pH is 8~12.

Preferably, it is room temperature~100 DEG C that the insulation reaction of step (4), which stops temperature, and the reaction predetermined time is 1~10h.

Preferably, sulfide is vulcanized sodium, potassium sulfide, sodium bisulfide, one or more kinds of mixtures in potassium hydrogen sulfide.

Preferably, oxidant be hydrogen peroxide, sodium peroxide, potassium peroxide, calper calcium peroxide, peromag, barium peroxide, Sodium hypochlorite, sodium sulfite, sodium hydrogensulfite, potassium sulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, persulfuric acid Sodium, hydrogen persulfate sodium, potassium peroxydisulfate, potassium hydrogen persulfate, ammonium persulfate, SODIUM PERCARBONATE, potassium percarbonate, sodium perborate, perboric acid One or more kinds of mixtures in potassium.

Preferably, stabilizer is alkyl phenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, aliphatic acid polyethenoxy Ester, polyoxyethylene amine, Pluronic F68, one or more kinds of mixtures in polyvinyl alcohol.

Preferably, ferrous salt be ferrous sulfate, it is ferrous nitrate, frerrous chloride, one or more kinds of in iron ammonium sulfate Mixture.

Preferably, step (3) is sodium hydroxide, hydrogen-oxygen agent, ammonium hydroxide, sodium carbonate, potassium carbonate, carbon for adjusting the alkali of pH One or more kinds of mixtures in sour hydrogen sodium, saleratus.

Beneficial effects of the present invention:

1, a heavy metal species processing of the method for the present invention manufacture with magnetic Nano Fe-S material to the adsorptivity of heavy metal and Reproducibility is strong, can be quickly by the free heavy metal adsorption in environment to material surface, and restores its toxicity of reduction；

2, the heavy metal species processing of the method for the present invention manufacture is strong with magnetic Nano Fe-S magnetism of material, and Magneto separate is good, It is separated by solid-liquid separation rapidly and efficiently, save the cost and reduction energy consumption；

3, the heavy metal species processing of the method for the present invention manufacture is simple with magnetic Nano Fe-S material preparation process, raw material Safety and environmental protection, it is low in cost, it not can cause environmental pollution.

4, the heavy metal species processing magnetic Nano Fe-S materials'use simple process of the method for the present invention manufacture, without adjusting Soda acid is saved, and fundamentally removes heavy metal from environment, avoids the risk of secondary pollution.

Detailed description of the invention

The following further describes the present invention with reference to the drawings.

Fig. 1 magnetic Nano Fe-S material preparation flow figure

Fig. 2 magnetic Nano Fe-S material prepares schematic diagram

1- ferrous salt；2- sulfide；3- oxidant；4- lye；5- chemical feed pipe；6- control valve；7- heating rod；8-pH meter； 9- aeration plate；10- water+stabilizer

1 magnetism of material of table and dispersion stabilization

2 material hexavalent chromium-treatments effect assessment of table

Specific embodiment

The present invention will be further described with reference to the examples below.Described embodiment and its result are merely to illustrate The present invention, without the present invention described in detail in claims should will not be limited.

Nine water vulcanized sodium: traditional Chinese medicines, reagent

NaHS: traditional Chinese medicines, reagent

Iron dichloride tetrahydrate: traditional Chinese medicines, reagent

Green vitriol: traditional Chinese medicines, reagent

Hydrogen peroxide: traditional Chinese medicines, 30%

Sodium hydrogensulfite: traditional Chinese medicines, reagent

Sodium hydroxide: traditional Chinese medicines, reagent

Polyvinyl alcohol: traditional Chinese medicines, 2000

Water: deionized water