CN102989427A - Enteromorpha absorbent and preparation technology thereof - Google Patents

Enteromorpha absorbent and preparation technology thereof Download PDF

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CN102989427A
CN102989427A CN2012105628520A CN201210562852A CN102989427A CN 102989427 A CN102989427 A CN 102989427A CN 2012105628520 A CN2012105628520 A CN 2012105628520A CN 201210562852 A CN201210562852 A CN 201210562852A CN 102989427 A CN102989427 A CN 102989427A
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enteromorpha
adsorbent
heavy metal
sodium chloride
chloride solution
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CN102989427B (en
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高宝玉
赵爽
岳钦艳
王燕
李倩
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Shandong University
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Abstract

The invention relates to an enteromorpha absorbent and a preparation technology of the enteromorpha absorbent. The preparation technology comprises the following steps of: washing and drying enteromorpha, grinding in a grinder, sieving with a sieve with 40-100 meshes, mixing the obtained enteromorpha dry powder and 0.1-0.5mol/L of sodium chloride or calcium chloride solution according to a mass ratio of 1:150-200, stirring and extracting for 6-8h at the thermostatic waterbath of 25-30 DEG C; and drying filter cakes for 3-4h in a drying oven with the temperature of 60-70 DEG C after decompression suction filtration to obtain the enteromorpha absorbent. The enteromorpha absorbent provided by the invention is applied to adsorption treatment of heavy metal wastewater, and can be used for effectively removing heavy metal ions in the wastewater. The preparation technology is low in cost, simple in a production technology, wide in application range, and safe and non-toxic, and solves the problem of disaster green alga enteromorpha recycling.

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 7-10m 2/ 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
Figure BDA00002634482700031
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 (5)

1. Enteromorpha adsorbent, measuring its granularity in the time of 20 ℃ is 0.15-0.45mm, specific area is 7-10m 2/ 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.
2. the preparation method of the described Enteromorpha adsorbent of claim 1, 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.
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.
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103319745A (en) * 2013-06-18 2013-09-25 青岛大学 Preparation method of enteromorpha full-component foam material
CN103962097A (en) * 2014-04-02 2014-08-06 中国石油大学(华东) Method for preparing CO2 carbon-based absorbent on basis ofenteromorpha
CN104056607A (en) * 2014-06-16 2014-09-24 李美凤 Enteromorpha gel oil suction material and preparation method thereof
CN104226243A (en) * 2013-06-18 2014-12-24 中国石油天然气股份有限公司 Preparation method of enteromorpha-based novel carbon material
CN104370324A (en) * 2014-03-25 2015-02-25 中国科学院海洋研究所 Method for adsorbing heavy metal ions in environment by utilizing macroalgae
CN105854820A (en) * 2016-04-12 2016-08-17 国家海洋局第海洋研究所 Preparation technology for enteromorpha for ship domestic sewage treatment
CN105903761A (en) * 2016-04-12 2016-08-31 国家海洋局第海洋研究所 A novel soil restoring carpet and a method of restoring soil by utilizing the carpet
CN106000348A (en) * 2016-08-01 2016-10-12 广西南宁桂尔创环保科技有限公司 Preparation method of adsorbent for treating zinc-containing wastewater
CN106140106A (en) * 2016-08-22 2016-11-23 青岛引黄济青水务有限责任公司 A kind of method utilizing Entermorpha to prepare water body fluoride removal material
CN106186156A (en) * 2016-08-01 2016-12-07 广西南宁桂尔创环保科技有限公司 A kind of method preparing arsenic-removing adsorption agent
CN107601640A (en) * 2017-11-09 2018-01-19 钦州学院 One kind crosslinking Enteromorpha xanthates high polymer coagulant and its preparation method and application
CN108404877A (en) * 2018-04-04 2018-08-17 青岛大学 A kind of methods for making and using same of Enteromorpha absorbent for wastewater treatment
CN109987690A (en) * 2019-04-02 2019-07-09 江苏师范大学 A kind of algal polysaccharides base composite water disposal agent and the preparation method and application thereof
CN110105960A (en) * 2019-04-29 2019-08-09 鲁东大学 A kind of acid soil cadmium, copper, zinc activator and preparation method thereof
CN111514854A (en) * 2020-05-01 2020-08-11 合肥学院 Preparation method of modified 3D porous carbon composite adsorption material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102417225A (en) * 2011-10-18 2012-04-18 山东大学 Enteromorpha flocculant and preparation process thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102417225A (en) * 2011-10-18 2012-04-18 山东大学 Enteromorpha flocculant and preparation process thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
S. K. MEHTA ET AL.: "Use of Algae for Removing Heavy Metal Ions From Wastewater: Progress and Prospects", 《CRITICAL REVIEWS IN BIOTECHNOLOGY》 *
郭赣林等: "浒苔对重金属Cu2+、Cd2+的生物吸附及其生理反应", 《海洋环境科学》 *
陈小梅等: "浒苔吸附废水中Pb2+的性能及其影响因素", 《材料保护》 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104226243A (en) * 2013-06-18 2014-12-24 中国石油天然气股份有限公司 Preparation method of enteromorpha-based novel carbon material
CN103319745B (en) * 2013-06-18 2015-03-04 青岛大学 Preparation method of enteromorpha full-component foam material
CN103319745A (en) * 2013-06-18 2013-09-25 青岛大学 Preparation method of enteromorpha full-component foam material
CN104370324A (en) * 2014-03-25 2015-02-25 中国科学院海洋研究所 Method for adsorbing heavy metal ions in environment by utilizing macroalgae
CN103962097A (en) * 2014-04-02 2014-08-06 中国石油大学(华东) Method for preparing CO2 carbon-based absorbent on basis ofenteromorpha
CN104056607A (en) * 2014-06-16 2014-09-24 李美凤 Enteromorpha gel oil suction material and preparation method thereof
CN105903761B (en) * 2016-04-12 2021-03-30 自然资源部第一海洋研究所 Soil remediation carpet and method for soil remediation by using same
CN105854820A (en) * 2016-04-12 2016-08-17 国家海洋局第海洋研究所 Preparation technology for enteromorpha for ship domestic sewage treatment
CN105903761A (en) * 2016-04-12 2016-08-31 国家海洋局第海洋研究所 A novel soil restoring carpet and a method of restoring soil by utilizing the carpet
CN106000348A (en) * 2016-08-01 2016-10-12 广西南宁桂尔创环保科技有限公司 Preparation method of adsorbent for treating zinc-containing wastewater
CN106186156A (en) * 2016-08-01 2016-12-07 广西南宁桂尔创环保科技有限公司 A kind of method preparing arsenic-removing adsorption agent
CN106140106B (en) * 2016-08-22 2019-07-12 青岛引黄济青水务有限责任公司 A method of water body fluoride removal material is prepared using Enteromorpha
CN106140106A (en) * 2016-08-22 2016-11-23 青岛引黄济青水务有限责任公司 A kind of method utilizing Entermorpha to prepare water body fluoride removal material
CN107601640A (en) * 2017-11-09 2018-01-19 钦州学院 One kind crosslinking Enteromorpha xanthates high polymer coagulant and its preparation method and application
CN108404877A (en) * 2018-04-04 2018-08-17 青岛大学 A kind of methods for making and using same of Enteromorpha absorbent for wastewater treatment
CN109987690A (en) * 2019-04-02 2019-07-09 江苏师范大学 A kind of algal polysaccharides base composite water disposal agent and the preparation method and application thereof
CN110105960A (en) * 2019-04-29 2019-08-09 鲁东大学 A kind of acid soil cadmium, copper, zinc activator and preparation method thereof
CN111514854A (en) * 2020-05-01 2020-08-11 合肥学院 Preparation method of modified 3D porous carbon composite adsorption material

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