CN102989427A

Movatterモバイル変換

Info

Publication number: CN102989427A
Application number: CN2012105628520A
Authority: CN
Inventors: 高宝玉; 赵爽; 岳钦艳; 王燕; 李倩
Original assignee: Shandong University
Current assignee: Shandong University
Priority date: 2012-12-22
Filing date: 2012-12-22
Publication date: 2013-03-27
Anticipated expiration: 2032-12-22
Also published as: CN102989427B

Abstract

本发明涉及浒苔吸附剂及其制备工艺。将浒苔洗净烘干后在粉碎机中粉碎，过40-100目筛，所得浒苔干粉与0.1-0.5mol/L的氯化钠或氯化钙溶液，以1：150-200质量比混合，在25－30℃恒温水浴中搅拌浸提6-8h；减压抽滤后，滤饼在60-70℃烘箱中烘干3-4h，得浒苔吸附剂。本发明浒苔吸附剂应用于重金属废水的吸附处理，可有效去除水中重金属离子。本发明成本低廉、生产工艺简单、适用范围广、安全无毒，并解决了灾害绿藻浒苔的再利用问题。The invention relates to an enteromorpha adsorbent and a preparation process thereof. Wash and dry Enteromorpha, pulverize it in a pulverizer, pass through a 40-100 mesh sieve, and mix the obtained Enteromorpha dry powder with 0.1-0.5mol/L sodium chloride or calcium chloride solution at a mass ratio of 1:150-200 Mix, stir and extract in a constant temperature water bath at 25-30°C for 6-8h; after vacuum filtration, dry the filter cake in an oven at 60-70°C for 3-4h to obtain the enteromorpha adsorbent. The enteromorpha adsorbent of the invention is applied to the adsorption treatment of heavy metal wastewater, and can effectively remove heavy metal ions in water. The invention has the advantages of low cost, simple production process, wide application range, safety and non-toxicity, and solves the problem of reuse of the disaster green alga Enteromorpha.

Description

A kind of Enteromorpha adsorbent and preparation technology thereof

(1) technical field

The present invention relates to a kind of Enteromorpha adsorbent and preparation technology thereof, belong to the processing of disaster green alga and recycling and water treatment agent technical field.

(2) background technology

Along with developing rapidly of industrial or agricultural, China's water resource has been subject to pollution in various degree, and increasing trend is arranged.For saving water resource, improve the utilization rate of water, alleviate the waste water pollution on the environment, we must strengthen the processing to waste water.Heavy metal wastewater thereby is common in plating, electronics industry and metallurgical industry, especially electroplates, electronics industry waste water, and its composition is very complicated, and for many years, the processing of heavy metal wastewater thereby is a difficult problem always.Present modal processing method is the precipitation method, physical-chemical process and biochemical process, and is wherein typical with chemiadsorption.But the costs such as existing adsorbent such as active carbon are expensive, and the preparation process conditional request is harsh, and it is larger to consume the energy, and can produce pollution, therefore, the low cost of development of new, efficiently, the adsorbent of safety non-toxic has very important significance for heavy metal containing wastewater treatment.

CN1431042A discloses modified fly ash absorbent and has used the method for its sorbent treatment waste water, chooses flyash 35～70 weight portions that granularity meets GB1596-91, adds sulfuric acid 30～60 weight portions of 0.5～3M, mixing and stirring; Then in 62～90 ℃ of activation 1～3 hour; Waste water adds above-mentioned adsorbent in the ratio of 0.5～2% percentage by weight, stirs precipitate and separate 2～30 minutes.Waste water after the processing, CODCr＜100, clearance reaches more than 78%, colourity＜20, clearance reaches more than 95%.

CN102698707A discloses a kind of industrial wastewater adsorbent and preparation method thereof, and the chemical composition of this adsorbent by weight percentage is formed by 80～95% slag fine powders, 2～15% water and 2～6% blowing agent combination than meter.The method step is: the percentage ratio is got 80～95% slag fine powders and 2～15% water and is stirred 8～12min with 100～200r/min at first by weight; The stirring thing that obtains stirring; Then percentage obtains mixture than adding 2～6% blowing agents to stirring in the thing by weight; Mixture is carried out pelletizing, and the bead of making is adsorbent.The present invention can realize the recycling of slag.

Enteromorpha belongs to green algae, is a genus of Chlorophyta Ulvaceae, extensively is distributed in each ocean, the whole world.Breaking out of Enteromorpha not only had a strong impact on the marine eco-environment, but also caused huge marine economy loss.Expend Enteromorpha major part after a large amount of manpower and materials establishment officers and Large-Scale Equipment are cleared up in the suburb air storage, cause the waste of resource and the energy.Therefore solving environment, the ecological problem that ocean Enteromorpha disaster brings is the needs of recycling economy and sustainable development.Also openly do not report about the technology of utilizing Enteromorpha to prepare the sorbent treatment heavy metal wastewater thereby through retrieving at present.

(3) summary of the invention

For the deficiencies in the prior art, the invention provides Enteromorpha adsorbent of a kind of quick, simple, cheap, environmental protection and preparation method thereof.The shortcoming such as high with the cost that overcomes prior art, that energy consumption is high, seriously polluted.

Technical scheme of the present invention is as follows:

A kind of Enteromorpha adsorbent, measuring its granularity in the time of 20 ℃ is 0.15-0.45mm, specific area is 7-10m²/ g is to make by the following method:

Enteromorpha is cleaned the rear pulverizing of oven dry, gained Enteromorpha powder is mixed with the sodium chloride of 0.1-0.5mol/L or the calcium chloride solution of 0.1-0.5mol/L, 1 weight portion Enteromorpha powder adds the described sodium chloride of 150-200 weight portion or calcium chloride solution, in 25-30 ℃ of water bath with thermostatic control, stir 6-8h, decompress filter, the filter cake oven dry, and get final product.

According to the present invention, a kind of preparation method of described Enteromorpha flocculant, step is as follows:

(1) Enteromorpha is cleaned, dries 4-8h in 60-70 ℃ of baking oven with running water; Enteromorpha after the oven dry is pulverized in pulverizer, crosses the 40-100 mesh sieve, and gained Enteromorpha dry powder is for subsequent use;

(2) sodium chloride of preparation 0.1-0.5mol/L or the calcium chloride solution of 0.1-0.5mol/L, with Enteromorpha: the mass ratio of sodium chloride or calcium chloride solution=1:150-200, the Enteromorpha dry powder of step (1) is added in the sodium chloride or calcium chloride solution of preparation stirring and leaching 6-8h in 25-30 ℃ of water bath with thermostatic control;

(3) solution after the lixiviate carries out decompress filter, and filter cake is dried 3-4h in 60-70 ℃ of baking oven, get the Enteromorpha adsorbent.

The application of Enteromorpha adsorbent of the present invention is used for heavy metal containing wastewater treatment.Particularly, the application of Enteromorpha adsorbent of the present invention is for the heavy metal containing wastewater treatment of leaded and/or cadmium.

The application of Enteromorpha adsorbent of the present invention as novel water treatment agent, can be used separately the processing heavy metal wastewater thereby, can be widely used in electroplating, the adsorption treatment of electronics and the industry such as metallurgical.

Such as the application with above-mentioned Enteromorpha adsorbent, consumption was 1-2g/L waste water when the Enteromorpha adsorbent was applied to separately the heavy metal containing wastewater treatment of leaded and/or cadmium.

Enteromorpha adsorbent of the present invention is applied to water treatment field and compares with existing adsorbent and have following excellent results:

1, Enteromorpha adsorbent of the present invention belongs to natural macromolecule adsorbent in the water treatment field, that Enteromorpha take periodically outburst is as raw material, adopt simple preprocess method to be prepared from, the Enteromorpha adsorbent is used for adsorption treatment heavy metal wastewater thereby process, the effectively heavy metal ion in the adsorbed water.Preparation technology of the present invention is simple, and preparation speed is fast, and raw material is sufficient, and is cheap, can be widely used in electroplating, the wastewater treatment of electronics and the industry such as metallurgical, has solved the energy consumption height and the problem of environmental pollution that produce in traditional absorbent preparation process.Simultaneously, also the Enteromorpha disaster for regularly outburst provides the approach that utilizes, and has realized refuse reclamation.

2, the present invention will be applied to the heavy metal containing wastewater treatment process as a kind of adsorbent through pretreated Enteromorpha powder, and the loose structure of Enteromorpha can be heavy metal effectively adsorption site is provided.Simultaneously, Enteromorpha is rich in the multiple macromolecular substances such as protein, polysaccharide and crude fibre, contains hydroxyl, carboxyl and the amido functional group of capacity, can comparatively completely complex reaction occur with heavy metal ion, thereby reach good adsorption effect.

(4) description of drawings

Fig. 1 is the product stereoscan photograph (amplifying 1,000 times) of embodiment 1.

(5) specific embodiment

The present invention will be further described below in conjunction with embodiment.Used Enteromorpha is taken from the Qingdao No.One Bathing Beach among the embodiment.

Embodiment 1:

Enteromorpha is cleaned, place 70 ℃ of baking oven 4h oven dry after, in the magnetic force pulverizer, be ground into powder, cross 100 mesh sieves, get Enteromorpha powder dry sample, for subsequent use.The sodium chloride solution of preparation 0.2mol/L mixes stirring and leaching 6h in 25 ℃ of waters bath with thermostatic control with the sodium chloride solution of Enteromorpha powder dry sample and 0.2mol/L with the mass ratio of 1:150.After solution after the lixiviate carried out decompress filter, filter cake got the Enteromorpha adsorbent at 70 ℃ of lower oven dry 4h.Recording average pore size by the specific surface area analysis instrument is 7.8-9.4nm.

Embodiment 2:

Enteromorpha is cleaned, place 70 ℃ of baking oven 6h oven dry after, in the magnetic force pulverizer, be ground into powder, cross 40 mesh sieves, get Enteromorpha powder dry sample, for subsequent use.The calcium chloride solution of preparation 0.5mol/L mixes stirring and leaching 8h in 25 ℃ of waters bath with thermostatic control with the calcium chloride solution of Enteromorpha powder and 0.5mol/L with the mass ratio of 1:200.After solution after the lixiviate carried out decompress filter, filter cake got the Enteromorpha adsorbent at 60 ℃ of lower oven dry 4h.

Above-mentioned Enteromorpha adsorbent is directly applied to the simulated wastewater that the heavy metal containing wastewater treatment process is processed heavy metal lead and cadmium, obtained better effects.

Experimental example 1:

Use the Enteromorpha adsorbent of embodiment 1 for the treatment of the heavy metal wastewater thereby water sample, use plumbi nitras to be dissolved in simulation lead contamination waste water in the deionized water.

The Enteromorpha adsorbent of preparation among the embodiment 1 is used for the processing of lead at different concentrations pollutant effluents, the Enteromorpha dosage is 1g/L, after adding the Enteromorpha adsorbent in the heavy metal simulated wastewater, concussion absorption 3h in 25 ℃ of water bath with thermostatic control oscillators, acquired results is listed in table 1 after the absorption.

The effect of table 1 Enteromorpha sorbent treatment lead contamination simulated water sample

From above result as seen, under the dosage of 1g/L, Enteromorpha sorbent treatment lead ion simulated water sample, under low concentration and high concentration, all has preferably adsorption effect, and adsorbance increases along with the increase of pollutant levels, be suitable for processing the high concentration heavy metal polluted waste water, its adsorption effect is better than traditional adsorbents such as commercially available active carbon.

Experimental example 2:

Use the Enteromorpha adsorbent of embodiment 2 for the treatment of the heavy metal wastewater thereby water sample, use caddy to be dissolved in and simulate cadmium polluted wastewater in the deionized water.

The Enteromorpha adsorbent of preparation among the embodiment 2 is used for the processing of variable concentrations cadmium polluted wastewater, and the Enteromorpha dosage is 1g/L, add Enteromorpha in the heavy metal simulated wastewater after, concussion absorption 3h in 25 ℃ of water bath with thermostatic control oscillators, acquired results is listed in table 2 after the absorption.

The effect of table 2 Enteromorpha sorbent treatment cadmium pollution simulated water sample

From above result as seen, the Enteromorpha adsorbent is under the dosage of 1g/L, process the cadmium ion simulated water sample, under low concentration and high concentration, all has preferably adsorption effect, particularly under low consistency conditions, clearance to heavy metal cadmium can reach 90%, and its adsorption effect is better than traditional adsorbents such as commercially available active carbon.

Claims

1. Enteromorpha adsorbent, measuring its granularity in the time of 20 ℃ is 0.15-0.45mm, specific area is 7-10m²/ g is to make by the following method:

2. the preparation method of the described Enteromorpha adsorbent of claim 1, step is as follows:

3. the application of the described Enteromorpha adsorbent of claim 1 is used for heavy metal containing wastewater treatment.

4. the application of the described Enteromorpha adsorbent of claim 1 is for the heavy metal containing wastewater treatment of leaded and/or cadmium.

5. the as claimed in claim 4 application of Enteromorpha adsorbent, consumption is 1-2g/L waste water when it is characterized in that the Enteromorpha adsorbent is applied to separately the heavy metal containing wastewater treatment of leaded and/or cadmium.