CN106698611A - Method for removing manganese ions in water through electro-adsorption - Google Patents

Method for removing manganese ions in water through electro-adsorption Download PDF

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Publication number
CN106698611A
CN106698611A CN201710030619.0A CN201710030619A CN106698611A CN 106698611 A CN106698611 A CN 106698611A CN 201710030619 A CN201710030619 A CN 201710030619A CN 106698611 A CN106698611 A CN 106698611A
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China
Prior art keywords
carbon fiber
activated carbon
water
electro sorb
manganese ion
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CN201710030619.0A
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Chinese (zh)
Inventor
魏永
赵威
徐斓
江晓栋
姚维昊
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Changzhou University
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Changzhou University
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Priority to CN201710030619.0A priority Critical patent/CN106698611A/en
Publication of CN106698611A publication Critical patent/CN106698611A/en
Pending legal-status Critical Current

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    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4691—Capacitive deionisation
    • 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
    • C02F2101/206—Manganese or manganese compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention relates to a method in the technical field of water treatment, and specifically relates to a method for removing manganese ions in water by taking acidized activated carbon fiber as an electrode material to perform electro-adsorption. The method is realized through the following technical schemes and specifically comprises the following steps: (1) performing hydrochloric acid modification treatment on an activated carbon fiber electrode; (2) assembling an electro-adsorption module of the activated carbon fiber electrode; and (3) performing adsorption and desorption on the manganese iond in water by changing the working voltage, water inlet flow and water inlet manganese ion concentration condition of the electro-adsorption module. The method disclosed by the invention has the advantages that the acidizing method of the activated carbon fiber electrode is simple and easy to implement, free from secondary pollution to the environment and easy to manufacture, the activated carbon fiber electrode has high adsorption efficiency to the manganese ions in water, the operation is simple, and the activated carbon fiber electrode can be continuously and cyclically used.

Description

A kind of method that Electro Sorb removes manganese ion in water removal
Technical field
The present invention relates to a kind of method of water-treatment technology field, specifically by the use of souring activity Carbon fibe as electrode material Material Electro Sorb removes Mn in water removal2+The method of ion, the method removal rate is fast, does not produce secondary pollution.
Background technology
In industrial aspect, such as weaving, printing and dyeing, papermaking, bleaching powder and film industry contain manganese higher in rinsing water The color and luster of product can be then reduced, the vividness of its color is influenceed.Using manganese containing water as food and brewing water, will have a strong impact on Color of food etc..When in water manganese content exceed certain value when, will also cause production equipment break down and cannot be normal Operation.In terms of water supply and sewerage pipeline, manganese content is high in water, and manganese can be deposited on tube wall and reduce the water passing capacity of pipeline, and it sinks Shallow lake is peeled off or manganese is when pipe end produces accumulation, will be had a strong impact on water supply quality and is blocked pipeline, increases resistance to water-flow, i.e., So-called " Heisui River " or " yellow water " are formed, the corrosion failure of pipeline can be also caused when serious.Mn-bearing waste water enters Drinking Water In, because the peculiar smell of manganese in water is larger, pollute living utensil, make people cannot normally using and can cause slow poisoning, China Manganese content in water is limited in below 0.1mg/L by drinking water standard.Mn-bearing waste water can be to the soil on periphery and ecological environment Cause harm.The intake of Excessive Manganese can cause animal and plant to be poisoned, and be mainly shown as and the nervous system of humans and animals is produced Poison.The general ventilating permeable in the discarded ground of slag is poor, easily causes surface pond, causes plant root histanoxia, adds soil The murder by poisoning of heavy metal manganese, plant growth is seriously obstructed.
Capacitive deionization (capacitive deionization, CDI), also known as Electro Sorb (electrosorption), is A kind of new type water that water intermediate ion and charged particle, purifying water body intermediate ion and charged particle are adsorbed using powered electrode surface Treatment technology, its advantage is：Removal process is not related to redox reaction, and energy consumption is low；Electrode after adsorption saturation can be by applying Plus backward voltage or the mode of short circuit are regenerated, regenerative operation is easy；Go during deionization that other auxiliary materials need not be added Material, does not produce secondary pollution；Do not have to chemically react in whole removal and regenerative process, electrode life is long.Therefore phase Than in traditional demanganization handling process, capacitive deionization technology is preceding in the great application of the application field containing heavy metal containing wastewater treatments such as manganese Scape.
NACF is that a kind of intensity is big, density is small, corrosion resistant novel metalloid material.Due to NACF tool There is specific surface area big, porous body product is big and the features such as small resistivity, necessarily applied as electric adsorption electrode material.It is living Property Carbon fibe there is continuous block structure, can be directly used as electric adsorption electrode, therefore manufacture craft and reduction can be simplified making Use cost.
The content of the invention
The method that a kind of Electro Sorb of present invention design removes manganese ion in water removal, including step in detail below：
(1) NACF acidification：Salt acid soak is used, substantial amounts of deionized water rinsing is then used, until pH value is Neutrality, conductivity value is less than 5 μ Scm-1.110 DEG C of drying in baking oven are positioned over, are placed in drier and are obtained souring activity Carbon fiber Dimension；
(2) Activated Carbon Fiber Electrodes are prepared：Souring activity Carbon fibe in step (1) is cut into block size to be lived Property Carbon fibe electrode；
(3) Electro Sorb goes water removal during the Activated Carbon Fiber Electrodes assembling that will be obtained in step (2) is arranged on electric adsorption module Middle manganese ion；
(4) Electro Sorb method removes manganese ion in water removal：Manganese ion solution again is configured, manganese ion solution is measured in beaker, incited somebody to action The Activated Carbon Fiber Electrodes electric adsorption module assembled in step (3) carries out Electro Sorb experiment.Electro Sorb experiment utilizes peristaltic pump The manganese ion solution extracted in beaker enters into electric adsorption module, is finally recycled in beaker, while real-time using conductivity meter The change of electrical conductivity in monitoring solution, when electrical conductivity keeps constant, i.e., Activated Carbon Fiber Electrodes reach adsorption equilibrium.
(5) desorption and regeneration of Activated Carbon Fiber Electrodes：When Activated Carbon Fiber Electrodes reach adsorption saturation, electric suction will be applied to Voltage short circuit or removal in attached module, the electrical conductivity in solution will be gradually restored to initial value, and electrode has obtained desorption and regeneration.
The concentration of the hydrochloric acid described in step (1) is 1molL-1, soak time is 3h, and pH value is close to 6.9.
Activated Carbon Fiber Electrodes size described in step (2) is 5cm × 5cm.
The metal ion that Activated Carbon Fiber Electrodes Electro Sorb described in step (3) is gone in water removal is Mn2+。
Heavy metal ion Mn described in step (4)2+Concentration be 100mg/L, operating voltage is 1.4V, and flow of inlet water is 15ml/min。
The advantage of the invention is that：Method is simple for NACF acidified modified, easily makes and environmental protection is without two Secondary pollution, has efficiency high by the use of modified Activated Carbon Fiber Electrodes as the electrode of electric adsorption module, simple to operate, material Easily it is obtained and the recycling performance of material has greatly improved with without modified material tool.
Brief description of the drawings
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1 is the modified scanning electron microscope (SEM) photograph (SEM figures) of the NACF prepared in embodiment one；
Fig. 2 is solution Mn in embodiment two2+Initial concentration is to Mn2+The influence of clearance；
Fig. 3 be embodiment three in operating voltage to Mn2+The influence of clearance；
Fig. 4 be example IV in flow of inlet water to Mn2+The influence of clearance；
Fig. 5 is the adsorption/desorption regeneration times of Activated Carbon Fiber Electrodes in embodiment five to being adsorbed in the influence of desorption rate.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out under premised on technical solution of the present invention Implement, give detailed implementation method, but protection scope of the present invention is not limited to following embodiments.
Embodiment one
The pretreatment of NACF：NACF is cut into the size of 5cm × 5cm, 1molL is used-1Hydrochloric acid Immersion 3h, to remove the ash content on NACF surface, then uses substantial amounts of deionized water rinsing, until pH value is neutrality, electricity Conductivity value is less than 5 μ Scm-1.110 DEG C of drying in baking oven are positioned over, are placed in drier.
Embodiment two
The acidified modified rear electrode production process of NACF is identical with embodiment one.
Electric adsorption module to Activated Carbon Fiber Electrodes composition carries out the experiment that Electro Sorb removes manganese ion in water removal.Electricity is inhaled Attached experiment condition is arranged to voltage for 1.0V, and flow of inlet water is 10mL/min, and pole plate spacing is controlled under conditions of 1mm, respectively Have studied manganese ion initial concentration NACF Electro Sorb in 150mg/L, 120mg/L, 100mg/L, 70mg/L and remove demanganization The effect of ion.Experimental result is as shown in Figure 2, it is seen that modified activated fibre electrode pair Mn2+With preferable adsorption effect.
Embodiment three
The acidified modified rear electrode production process of NACF is identical with embodiment one.
It is the manganese ion solution of 150mg/L to choose initial concentration, and electrode spacing is isolated by being clipped in two interelectrode non-woven fabrics, Spacing is controlled in 1mm, controls flow of inlet water for 10ml/min, and the work electricity of 0V, 1.0V, 1.2V, 1.4V, 1.6V is applied respectively Pressure, electric adsorption module is assembled into Activated Carbon Fiber Electrodes carries out Electro Sorb removal manganese ion experiment, as a result as Fig. 3 shows.It can be seen that Modified activated fibre electrode pair Mn in the case of operating voltage is suitable2+With preferable adsorption effect.
Example IV
The acidified modified rear electrode production process of NACF is identical with embodiment one.
Experiment condition have chosen manganese ion concentration for 100mg/L, and operating voltage is controlled in 1.4V, and electrode spacing is by being clipped in two Interelectrode non-woven fabrics isolation, spacing control have studied the adsorption effect of Activated Carbon Fiber Electrodes in 1mm.
Embodiment five
The acidified modified rear electrode production process of NACF is identical with embodiment one.
The electric adsorption electrode being made modified to NACF is circulated Electro Sorb experiment.By Activated Carbon Fiber Electrodes In electric adsorption module, applying operating voltage is 1.4V, and flow of inlet water control is desorbed concentration in 15ml/min circulation absorptions It is the Mn of 100mg/L2+Solution, calculates its adsorption rate and desorption rate.Experimental result is as shown in Figure 5.First time circulation absorption is desorbed After experiment, the adsorption rate of NACF is 52.54%, by after five circulation absorption detachment assays, clearance reduced by only 6.31%, illustrate that the material has high regenerability.

Claims (6)

1. a kind of method that Electro Sorb removes manganese ion in water removal, it is characterised in that specifically include following steps：
(1) NACF acidification：Salt acid soak is used, substantial amounts of deionized water rinsing is then used, until pH value is neutrality, Conductivity value is less than 5 μ Scm-1.110 DEG C of drying in baking oven are positioned over, are placed in drier and are obtained souring activity Carbon fibe；
(2) Activated Carbon Fiber Electrodes are prepared：Souring activity Carbon fibe in step (1) is cut into block size and obtains activated carbon Fiber electrode；
(3) Electro Sorb removes manganese in water removal during the Activated Carbon Fiber Electrodes assembling that will be obtained in step (2) is arranged on electric adsorption module Ion；
(4) Electro Sorb method removes manganese ion in water removal：Configuration manganese ion solution, measures manganese ion solution in beaker, by step (3) In the Activated Carbon Fiber Electrodes electric adsorption module that assembles carry out Electro Sorb experiment.Electro Sorb experiment utilizes peristaltic pump pumps beaker In manganese ion solution enter into electric adsorption module, be finally recycled in beaker, while using conductivity meter real-time monitoring solution The change of middle electrical conductivity, when electrical conductivity keeps constant, i.e., Activated Carbon Fiber Electrodes reach adsorption equilibrium.
(5) desorption and regeneration of Activated Carbon Fiber Electrodes：When Activated Carbon Fiber Electrodes reach adsorption saturation, Electro Sorb mould will be applied to Voltage short circuit or removal on block, the electrical conductivity in solution will be gradually restored to initial value, and electrode has obtained desorption and regeneration.
2. the method that a kind of Electro Sorb as described in claim 1 step removes manganese ion in water removal, it is characterised in that step (1) Described in hydrochloric acid concentration be 1molL-1, soak time is 3h, and pH value is close to 6.9.
3. the method that a kind of Electro Sorb as claimed in claim 1 removes manganese ion in water removal, it is characterised in that institute in step (2) The Activated Carbon Fiber Electrodes size stated is 5cm × 5cm.
4. the method that a kind of Electro Sorb as described in right 1 removes manganese ion in water removal, it is characterised in that the work described in step (3) Property Carbon fibe electrode Electro Sorb go water removal in heavy metal ion be Mn2+。
5. the method that a kind of Electro Sorb as described in right 1 removes barium ions in water removal, it is characterised in that the electricity described in step (3) The electrode logarithm of adsorption module is 3 pairs.
6. the method that a kind of Electro Sorb as described in right 1 removes manganese ion in water removal, it is characterised in that the weight described in step (4) Metal ions M n2+Concentration be 100mg/L, operating voltage is 1.4V, and flow of inlet water is 15ml/min.
CN201710030619.0A 2017-01-17 2017-01-17 Method for removing manganese ions in water through electro-adsorption Pending CN106698611A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103723801A (en) * 2014-01-03 2014-04-16 湖南农业大学 Combination electrode hydro-thermal synthesis method for removing arsenic in water based on electro-adsorption and arsenic removing method thereof
US20150299016A1 (en) * 2012-08-03 2015-10-22 Mitsubishi Heavy Industries Mechatronics Systems, Ltd. Water treatment device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150299016A1 (en) * 2012-08-03 2015-10-22 Mitsubishi Heavy Industries Mechatronics Systems, Ltd. Water treatment device
CN103723801A (en) * 2014-01-03 2014-04-16 湖南农业大学 Combination electrode hydro-thermal synthesis method for removing arsenic in water based on electro-adsorption and arsenic removing method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李海红 等: "盐酸预处理对ACF结构及其电化学性能的影响", 《材料科学与工程学报》 *
王翠 等: "活性炭纤维电极对不同阳离子电吸附行为的试验研究", 《中国新技术新产品》 *

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Application publication date: 20170524