CN109851028A - The minimizing technology of chloride in a kind of water - Google Patents
The minimizing technology of chloride in a kind of water Download PDFInfo
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- CN109851028A CN109851028A CN201910099531.3A CN201910099531A CN109851028A CN 109851028 A CN109851028 A CN 109851028A CN 201910099531 A CN201910099531 A CN 201910099531A CN 109851028 A CN109851028 A CN 109851028A
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Abstract
一种水中氯化物去除方法，先将氯离子转化为有机氯，再通过成本经济的方式去除所述有机氯。将氯离子氧化为活性氯，往其中添加有机物或含有有机物的实际水体，使得活性氯与所述有机物反应形成有机氯。是利用高级氧化工艺中产生的强氧化性的羟基自由基或硫酸根自由基将氯离子氧化为活性氯。在含有氯化物的水中加入氧化剂；对所述氧化剂激活以产生强氧化性的羟基自由基或硫酸根自由基；往其中添加有机物或含有有机物的实际水体，使得活性氯与所述有机物反应形成有机氯。本发明通过将无机氯化物转化为有机氯，有机氯更容易被常规工艺去除；操作简单，采用的试剂为环境友好型试剂，可以有效去除水中的氯离子，解决高含量氯化物水体治理困难的问题。
A method for removing chlorides in water, which firstly converts chloride ions into organic chlorine, and then removes the organic chlorine in a cost-effective manner. Chloride ions are oxidized to active chlorine, to which is added organic matter or an actual body of water containing organic matter so that the active chlorine reacts with the organic matter to form organochlorine. It uses the strong oxidizing hydroxyl radical or sulfate radical generated in the advanced oxidation process to oxidize the chloride ion into active chlorine. Add an oxidant to water containing chloride; activate the oxidant to generate strong oxidizing hydroxyl radicals or sulfate radicals; add organic matter or an actual water body containing organic matter to it, so that active chlorine reacts with the organic matter to form organic chlorine. The invention converts inorganic chloride into organic chlorine, and the organic chlorine is easier to be removed by conventional processes; the operation is simple, and the reagent used is an environment-friendly reagent, which can effectively remove chloride ions in water, and solves the problem of difficult treatment of high-chloride water bodies. question.
Description
Technical field
The invention belongs to water-treatment technology fields, are related to water middle and high concentration chloride removal method, are based especially on advanced
The water middle and high concentration chloride removal technology of oxidation technology (AOP).
Background technique
There are many advanced oxidation processes type, using also very extensive.Ultraviolet/hydrogen peroxide (UV/H2O2) it is a kind of typical advanced
Oxidation technology.H2O2Under the radiation of UV light, it is broken O-O key after absorbing luminous energy, generates the OH of strong oxidizing property, oxidation is also
Former current potential is 2.8V.OH is reacted with organic matter without selectivity, and organic pollutant can be oxidized to carbon dioxide, Shui Hekuang
Object salt, the rate constant reacted with most of organic matters is 106-1010L/ (mols), reaction speed is fast.UV/H2O2Oxidation has
The reaction of machine object is related to direct oxidation, the H of UV light2O2Or the oxidation of OH.OH is divided into three kinds instead to the oxidation of organic matter
It should carry out: dehydrogenation reaction, parent-offspring's addition and electronics transfer, wherein most importantly dehydrogenation reaction.
Fig. 1 is UV/H2O2Ultraviolet photolysis hydrogen peroxide generates the hydroxyl radical free radical of a large amount of high oxidative capacities in high-level oxidation technology
Schematic diagram.
UV/H2O2High-level oxidation technology can effective degradation of contaminant, before being widely used in terms of the drinking water advanced treatment
Scape.
Chloride (i.e. chloride ion) is widely present in natural water (i.e. sodium chloride, chlorination in the form of sodium, calcium and magnesium salts etc.
Calcium, magnesium chloride etc.), all there is chloride in almost all of surface water, but content difference is very big, the chloride in certain river waters
Concentration is only a few mg/litres, and the chloride (i.e. chloride ion [Cl in seawater-]) content is up to 19000mg/L.Work as seawater invasion
Drinking water source causes source water chloride exceeded or directly using the higher water of chloride content as when drinking water source, it is necessary to right
Chloride does some processing.High concentration chloride can not generally pass through the common process such as chemical precipitation, filtering, air bearing, absorption institute
Removal, reverse osmosis process with high costs and cumbersome can remove chloride to a certain extent, but application potential by
This institute limits.Therefore, it is necessary to seek, friendly to environment green, cost is controllable, safe and efficient high concentration chloride processing technique.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide one kind to remove in water removal chloride especially
It is the method for high concentration chloride；Further, a kind of method for removing water removal middle and high concentration chloride based on advanced oxidation is provided.
Technical thought of the invention is by being to be easier to by chemical precipitation, filtering, air bearing, absorption by inorganic chlorine ion conversion
The organochlorine that equal common process are removed, to achieve the purpose that remove chloride indirectly.Principle is: utilizing advanced oxidation processes
The hydroxyl radical free radical or potentiometric titrations (Fig. 1) of the strong oxidizing property of middle generation, chloride ion is oxidized to Active Chlorine, and (such as chlorine is free
Base etc., Fig. 2).Add the organic matters such as humic acid or the practical water body containing organic matter again, the chlorine in additive amount and treated water from
Sub- content is proportional, and Active Chlorine reacts to form organochlorine (Fig. 3) with the organic matter that these are added.Organochlorine can be with
Organic chloride is gone by the common process such as chemical precipitation, filtering, air bearing, absorption or other economic costs lower mode
It removes.
The specific method is as follows:
Hydrogen peroxide (H is added in high concentration chloride2O2) (including the oxidants such as persulfate, single persulfate, and will
The composite drug etc. that the above oxidant and each metal ion species are compounded to form, below by taking hydrogen peroxide as an example), added H2O2Solution
Amount according to the concentration of chloride determine.Under ultraviolet light reaction certain time by hydrogen peroxide be converted into hydroxyl radical free radical (in addition to
Except ultraviolet lighting, the oxidants such as hydrogen peroxide can also be activated to generation high oxidation by adding the modes such as the metal ions such as iron, manganese
Property hydroxyl radical free radical or potentiometric titrations etc.), the organic matters such as humic acid are added and (are not limited to humic acid, amino acid, protein
And the practical water body containing these organic matters all can), react certain time.
Preferably, chloride concentration is 100-20000mg/L in raw water.
Preferably, H2O2With chloride mole control within the scope of 1:10-10:1.Also, persulfate, single persulfate
Equal oxidants, and the composite drug etc. that the above oxidant and each metal ion species are compounded to form can be substituted into hydrogen peroxide,
The ratio between oxidizer composition (hydrogen peroxide, persulfate or single persulfate) and chloride mole in them need to only be controlled 1:
Within the scope of 10-10:1.
Preferably, the concentration of the organic matter (organic carbon content) in the raw water body after adding is 1-5mg/L.
Preferably, the temperature being protected from light is 20 ± 2 DEG C.
Preferably, the ultraviolet light lower reaction time is 1-100 minutes.
Preferably, ultraviolet light intensity control is in 1-1000 μ W/cm2。
Preferably, (organic carbon content) of humic acid and chloride mole are within the scope of 1:1-100:1.And it is not limited to corruption
Grow acid, the organic matters such as amino acid, protein and the practical water body containing these organic matters all can, need to only control these organic matters
Organic carbon content and chloride mole within the scope of 1:1-100:1.
Preferably, it controls with the reaction time of humic acid or other organic matters in 1-12h.
Due to the adoption of the above technical scheme, the invention has the following advantages:
Chloride (i.e. chloride ion) is difficult the conventional work by advantage of lower cost such as chemical precipitation, filtering, air bearing, absorption
Skill is removed, and inorganic chlorine ion conversion is creatively organochlorine by the present invention, to be easy to be removed by common process；
The added medicament of the present invention is environmentally protective, has cost relative to the chloride removals technology such as reverse osmosis controllably, no
Can generate reverse osmosis concentration waste water, it is easily operated the features such as；
Reaction condition is mild, applied widely.It is of the present invention to be gone needed for removing chloride reaction based on advanced oxidation
PH is 3-10, and reaction condition is mild.The pH of general natural water body is neutral or alkalescent, is pre-processed in water factory's actual implementation
When, without adjusting pH, save manpower, material resources and financial resources.
Detailed description of the invention
Fig. 1 is high-level oxidation technology schematic diagram (with UV/H2O2For).
Fig. 2 is that chloride is converted Active Chlorine schematic diagram by the hydroxyl radical free radical of strong oxidizing property.
Fig. 3 is that Active Chlorine reacts to form organochlorine schematic diagram with organic matter.
Specific embodiment
The present invention is further illustrated with reference to the accompanying drawings and embodiments.
Technical thought of the invention is by being to be easier to by chemical precipitation, filtering, air bearing, absorption by inorganic chlorine ion conversion
The organochlorine that equal common process are removed, to achieve the purpose that remove butter indirectly.Principle is: utilizing advanced oxidation
The hydroxyl radical free radical or potentiometric titrations (please referring to Fig. 1) of the strong oxidizing property generated in technique, are oxidized to activity for chloride ion
Chlorine (such as chlorine radical please refers to Fig. 2).The organic matters such as humic acid or the practical water body containing organic matter, additive amount are added again
It is proportional with the chloride ion content in treated water, Active Chlorine reacted with the organic matter that these are added to be formed it is organic
Chlorine (please refers to Fig. 3).Organochlorine can pass through the common process such as chemical precipitation, filtering, air bearing, absorption or other economic costs
Lower mode removes organic chloride.
A kind of method based on advanced oxidation removal high concentration chloride of the present invention comprising following steps:
Hydrogen peroxide (H is added in high concentration chloride2O2) (including the oxidants such as persulfate, single persulfate, and
The composite drug etc. that the above oxidant and each metal ion species are compounded to form, below by taking hydrogen peroxide as an example), added H2O2It is molten
The amount of liquid is determining according to the concentration of chloride, H2O2It is within the scope of 1:10-10:1 with chloride molar ratio.It reacts under ultraviolet light
(ultraviolet light intensity is controlled in 1-1000 μ W/cm within 1-100 minutes2), so as to by hydrogen peroxide be converted into hydroxyl radical free radical (in addition to
, can also be by oxidants such as hydrogen peroxide by adding the modes such as the metal ions such as iron, manganese except ultraviolet lighting), humic acid etc. is added
Organic matter, humic acid with chloride mole within the scope of 1:1-100:1, react 1-12h.It will by above-mentioned processing mode
Butter is converted into organochlorine, organochlorine be easier by common process removal (common process include coagulating sedimentation, filtering,
Air bearing, absorption etc., but not limited to this).
Chloride concentration is 100-20000mg/L in the raw water.
The oxidants such as persulfate, single persulfate, and the above oxidant and each metal ion species are compounded to form
Composite drug etc. can substitute hydrogen peroxide, need to only control oxidizer composition (hydrogen peroxide, persulfate or single over cure in them
Hydrochlorate) with the ratio between chloride mole within the scope of 1:10-10:1.
The organic matter of addition is not limited to humic acid, amino acid, protein and the practical water body containing these organic matters etc.
Organic matter all can, only need to control these organic matters organic carbon content and chloride mole within the scope of 1:1-100:1.
Basic principle of the invention is expressed as follows with equation:
H2O+H2O2+ ultraviolet light=OH (1)
OH+ chloride=Active Chlorine (2)
Active Chlorine+humic acid=organochlorine (3)
It goes to lead to shown in water removal middle and high concentration chloride principle such as equation (1), (2) and (3) the present invention is based on advanced oxidation
The hydroxyl radical free radical generated in advanced oxidation processes is crossed, chloride ion is oxidized to Active Chlorine (such as chlorine radical, hypochlorite).
Humic acid or the practical water body containing organic matter are added again, additive amount and the chloride ion content in treated water are proportional,
Active Chlorine reacts to form organic chloride with organic matter.The organic chloride of generation is easily removed compared to inorganic chloride ion, Ke Yitong
It crosses coagulating sedimentation or the lower mode of other economic costs removes organic chloride.
The present invention is further illustrated with reference to embodiments.
Embodiment 1:
The water middle and high concentration chloride removal new method based on advanced oxidation processes of the present embodiment includes the following steps:
The H of various concentration (1-20mM) is added in containing the water sample that chlorine ion concentration is 200mg/L2O2Solution, and consider
Different ultraviolet light intensity (100-500 μ W/cm2) ultraviolet light influence, react solution after taking after 1 hour 40mL to react and be added not
The humic acid of same concentration (20-200mg/L) is sealed with the screw lid with teflon gasket immediately, after being sufficiently mixed, is deposited
It is put in insulating box to be protected from light and detects water sample moderate water apparatus content of halogen afterwards for 24 hours.Compared by analysis of experimental results, is determined optimal
Under the conditions of conversion ratio.
Embodiment 2:
The water middle and high concentration chloride removal new method based on advanced oxidation processes of the present embodiment includes the following steps:
Sodium sulphate (the Na of various concentration (1-20mM) is added in containing the water sample that chlorine ion concentration is 150mg/L2S2O8)
Solution, and consider different ultraviolet light intensity (100-500 μ W/cm2) ultraviolet light influence, take 40mL to react after reacting 1 hour
The humic acid of various concentration (20-200mg/L) is added in solution afterwards, is sealed immediately with the screw lid with teflon gasket,
After being sufficiently mixed, deposits in insulating box to be protected from light and detect water sample moderate water apparatus content of halogen afterwards for 24 hours.Pass through analysis of experimental results
Compare, determines the conversion ratio under optimal conditions.
Embodiment 3:
The water middle and high concentration chloride removal new method based on advanced oxidation processes of the present embodiment includes the following steps:
The Potassium Monopersulfate of various concentration (1-20mM) is added in containing the water sample that chlorine ion concentration is 250mg/L
(2KHSO5.KHSO4.K2SO4) solution, and consider different ultraviolet light intensity (100-500 μ W/cm2) ultraviolet light influence, reaction 1
The humic acid of various concentration (20-200mg/L) is added in solution after taking 40mL to react after a hour, immediately with polytetrafluoroethylene (PTFE)
The screw lid of gasket seals, and after being sufficiently mixed, deposits in insulating box and is protected from light for 24 hours that detection water sample moderate water apparatus halogen contains afterwards
Amount.Compared by analysis of experimental results, determines the conversion ratio under optimal conditions.
To the products measure of above-described embodiment for 24 hours after organic halogen content, organic halogen measured by TOX instrument.
The conversion ratio of 1. butter of table
| Embodiment | Inorganic chlorine (mg/L) | Organochlorine (mg/L) | Optimal conversion (%) |
| Embodiment 1 | 200 | 95.6 | 47.8 |
| Embodiment 2 | 150 | 76.8 | 51.2 |
| Embodiment 3 | 250 | 116.7 | 46.7 |
As known from Table 1, the present invention is based on the technologies of advanced oxidation removal high-concentration chlorine ion can be effectively reduced in raw water
The concentration of chloride ion, removal rate can achieve 46.7-51.2%.
The above-mentioned description to embodiment is that this hair can be understood and used for the ease of those skilled in the art
It is bright.Those skilled in the art obviously readily can make various modifications to these embodiments, and described herein one
As principle be applied in other embodiments, without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments.
Those skilled in the art's principle according to the present invention, not departing from improvement that scope of the invention is made and modification all should be at this
Within the protection scope of invention.
Claims (13)
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| CN201910099531.3A CN109851028B (en) | 2019-01-31 | 2019-01-31 | Method for removing chloride in water |
| JP2019217660A JP6904525B2 (en) | 2019-01-31 | 2019-12-01 | How to remove chloride in water |
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Cited By (3)
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| CN110255799A (en) * | 2019-06-11 | 2019-09-20 | 中国科学院生态环境研究中心 | A kind of dechlorination medicament and the methods and applications that are dechlorinated using it to acid water |
| CN110921928A (en) * | 2019-10-24 | 2020-03-27 | 清华大学 | Method for treating coking wastewater concentrated solution by irradiation coupling peroxymonosulfate |
| CN112551760A (en) * | 2020-12-22 | 2021-03-26 | 上海鲲谷环保科技有限公司 | Method for removing iodine in wastewater |
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| CN116425355A (en) * | 2023-04-23 | 2023-07-14 | 浙江工业大学 | Dechlorination and removal method for trichlorophenol in nitrate-containing wastewater |
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| CN109851028B (en) | 2020-08-28 |
| JP2020124701A (en) | 2020-08-20 |
| JP6904525B2 (en) | 2021-07-21 |
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