CN109626547A - A method of using ferrous ion catalysis oxidation high concentration trivalent arsenic - Google Patents
A method of using ferrous ion catalysis oxidation high concentration trivalent arsenic Download PDFInfo
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- CN109626547A CN109626547A CN201811604612.6A CN201811604612A CN109626547A CN 109626547 A CN109626547 A CN 109626547A CN 201811604612 A CN201811604612 A CN 201811604612A CN 109626547 A CN109626547 A CN 109626547A
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- trivalent arsenic
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of method using ferrous ion catalysis oxidation high concentration trivalent arsenic, include the following steps: to mix the trivalent arsenic solution of 0.001g/L-50g/L with ferrous salt, adjusts pH to acidity；The mixed liquor obtained after pH will be adjusted to be added into autoclave, stir, after being heated to certain temperature, be passed through oxygen to certain partial pressure of oxygen；After reaction carries out a period of time, trivalent arsenic is oxidized to pentavalent arsenic in solution.The invention has the benefit that simple process, easy to operate, condition needed for reacting is easy to realize；Reaction is not required to special installation, and required autoclave is extremely common in the industry；Used reagent ferrous salt and oxygen are common materials in metallurgical industry, and cheap are easily obtained；In implementation process, in addition to ferric iron, other by-products are not generated, without complicated subsequent processes.
Description
Technical field
The present invention relates to hazardous waste processing technology fields, use ferrous ion catalysis oxidation more particularly, to a kind of
The method of high concentration trivalent arsenic.
Background technique
Arsenic is a kind of toxic element, and in Non-ferrous minerals, simple substance and compound have very strong poison for extensive association
Property and carcinogenicity.For decades, China's non-ferrous metals industry flourishes, while exploitation Non-ferrous minerals extensively, arsenic
Pollution problem is also more prominent.
Arsenic after nonferrous smelting system, the overwhelming majority enter pyrometallurgical smelting slag, flue dust, hydrometallurgy waste water, waste residue and
Electrolysis anode sludge.Currently used wet process Arsenic fixation method, such as lime neutralisation, sulfurization-precipitation method, iron arsenic coprecipitation, scorodite
Method etc. mainly for high arsenic concentration waste liquid, and has wide application when purifying hydrometallurgy waste water.Typically, for
Part cannot stablize the high-arsenic material of stockpiling, arsenic therein can be made to enter liquid with ionic forms by wet-leaching technique first
Phase obtains high concentration arsenic leaching solution, then is solidified via above method.Wet process consolidates method used in arsenic and is all based on As
(V) main object is mutually developed, these methods fix arsenic in the form of pentavalent compound.Because for As (III),
As (V) toxicity is lower, and migration is smaller, and the heavy arsenic mineral of As (V) is also universal relatively stable.And under normal circumstances, relieving haperacidity, smelting
In the faintly acid waste water of refining processing of copper electrolysis output, and the solution of processing smelting smoke dust output, contain a large amount of As
(III), it therefore before carrying out it solid arsenic, needs that As therein (III) is oxidized to As (V) in advance.
To improve As (III) oxidation rate, in high-arsenic material treatment process the oxidation of arsenic commonly rely on multiple pricing compared with
High and active property strong oxidizer, such as hydrogen peroxide, permanganate.Oxygen equally can be used as the oxidant of arsenic, and price is low
It is honest and clean to be easy to produce, but in no catalyst action, it reacts very slow.Common catalyst include manganese dioxide, potassium permanganate,
Ultraviolet light etc..The universal concentration of arsenious waste solution in metallurgical industry is in several gram liters even tens gram liters, and the pH value of waste liquid is all very
It is low, 1.0 are likely lower than, conventionally to be handled, needs to be added large quantities of lime preneutralization and improves pH value.If in not pre-
With, then it can not aoxidize, it is also very serious to the erosion of equipment, and the facilitation that ferrous salt catalyst aoxidizes trivalent arsenic at present is only
It is limited to the trivalent arsenic solution of mg/L rank, and under no hydrogen peroxide synergism, effect is undesirable, it is difficult to be suitable for a large amount of high
The centralized processing of concentration trivalent arsenic material.
Summary of the invention
Based on this, the present invention is only limitted to mg/L rank for the facilitation that catalyst aoxidizes trivalent arsenic in the prior art
Arsenious acid or arsenite solution, a kind of method using ferrous ion catalysis oxidation high concentration trivalent arsenic is provided.
The present invention is in order to solve the above technical problems, adopt the following technical scheme that
A method of using ferrous ion catalysis oxidation high concentration trivalent arsenic, include the following steps:
S1, the trivalent arsenic solution of 0.001g/L-50g/L is mixed with ferrous salt, adjusts pH to acidity；
S2, the mixed liquor obtained after adjusting pH in S1 is added into autoclave, stirs, after being heated to certain temperature, leads to
Enter oxygen to certain partial pressure of oxygen；
After S3, reaction carry out a period of time, trivalent arsenic is oxidized to pentavalent arsenic in solution.
The trivalent arsenic is selected from arsenious acid and/or arsenite in one of the embodiments,.
The arsenite is selected from one or both of sodium arsenite, potassium arsenite in one of the embodiments,.
In one of the embodiments, the ferrous salt be selected from one of ferrous sulfate, frerrous chloride, ferrous nitrate or
It is a variety of.
It is described acid for 0.1-2.5 in one of the embodiments,.
The volume ratio of the trivalent arsenic solution and ferrous salt is 0.1:1-20:1 in one of the embodiments,.
The pressure of the partial pressure of oxygen is 0.1-100Mpa in one of the embodiments,.
In one of the embodiments, in step s 2, the rate of the stirring is 100-1000rpm；The heating
Temperature is 50-300 DEG C.
In one of the embodiments, in step s3, reaction time 1-12h.
In one of the embodiments, in step sl, pH is adjusted using sulfuric acid, hydrochloric acid or nitric acid.
For the present invention by the way that ferrous salt is added in the trivalent arsenic solution to high concentration, oxygen is passed through in autoclave makes reactant
There is hyperbaric environment can promote ferrous oxidation in addition, heating into autoclave, improve ferrous oxygenation efficiency, greatly for system
The amount quick energy of oxidation of ferrous iron generates a large amount of hydroxyl radical free radical in a short time, and g/L concentration arsenious acid can just be promoted to send out in this way
Raw oxidation.Compared with the prior art, the invention has the following beneficial effects:
(1) simple process, easy to operate, equipment needed for reacting has been widely used in the industry.
(2) reagent ferrous salt and oxygen used in are common materials in metallurgical industry, and cheap are easily obtained.
(3) in implementation process, in addition to ferric iron, other by-products are not generated, without complicated subsequent processes.
(4) this method is suitable for processing high concentration trivalent arsenic, and is also suitable to the trivalent arsenic of low concentration, while being also suitable strong
Acid trivalent arsenic solution, provides a great convenience to metallurgical industry in this way, is of great significance.
Detailed description of the invention
Fig. 1 is the flow diagram of the method disclosed by the invention using ferrous ion catalysis oxidation high concentration trivalent arsenic；
Fig. 2 is that trivalent arsenic oxygenation efficiency changes with time figure in embodiment 1-5 disclosed by the invention.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.Many details are explained in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case where violating intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
Embodiment 1
Ferrous sulfate solution is mixed with arsenic chloride solution according to initial iron arsenic molar ratio 2:1, trivalent arsenic concentration after mixing
For 0.5g/L.Mixed liquor pH value is adjusted to 0.5 using sulfuric acid, is then moved into autoclave, is risen to 150 DEG C to reactor temperature
Afterwards, it is passed through 1MPa oxygen, and maintains 200rpm stirring rate that solution is at the uniform velocity sufficiently stirred.Reaction maintains 180min, during which every
60min is sampled, and is tested and analyzed to sample obtained by 60min, 120min and 180min.Resulting arsenious acid oxygenation efficiency point
It Wei 37.83%, 45.00%, 46.33%.
Embodiment 2
Arsenious oxide acid solution according to the method for embodiment 1.Oxygen pressure is changed to 0.5MPa, remaining condition and the complete phase of example 1
Together.Sample obtained by 60min, 120min and 180min is tested and analyzed.The oxygenation efficiency of resulting arsenious acid is respectively
13.19%, 25.26%, 30.02%.
Embodiment 3
Arsenious oxide acid solution according to the method for embodiment 1.Initial iron arsenic molar ratio is changed to 5:1, remaining condition and example 1
It is identical.Sample obtained by 60min, 120min and 180min is tested and analyzed.Resulting arsenious acid oxygenation efficiency is respectively
52.02%, 58.15%, 60.10%.
Embodiment 4
According to the method arsenious oxide acid solution of embodiment 3.Partial pressure of oxygen is changed to 1.5MPa, remaining condition and example 1 are complete
It is identical.Sample obtained by 60min, 120min and 180min is tested and analyzed.Resulting arsenious acid oxygenation efficiency is respectively
58.04%, 60.12%, 60.60%.
Embodiment 5
Arsenious oxide acid solution according to the method for embodiment 1.PH value of solution is formulated as 0.3, remaining condition and the complete phase of example 1
Together.Sample obtained by 60min, 120min and 180min is tested and analyzed.The oxygenation efficiency of resulting arsenious acid is respectively
18.64%, 26.91%, 28.84%.
Comparative example 1
Arsenious oxide acid solution according to the method for embodiment 1.It is 25 DEG C by temperature setting, remaining condition and the complete phase of example 1
Together.Sample obtained by 60min, 120min and 180min is tested and analyzed.Resulting arsenious acid in 60min, 120min,
Significantly aoxidizing does not occur in 180min.
In conclusion the acquired results of embodiment 1-5 are as shown in Fig. 2.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
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Cited By (3)
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|---|---|---|---|---|
| CN111573715A (en) * | 2020-06-16 | 2020-08-25 | 云南锡业研究院有限公司 | Method for preparing stannic oxide by using tin oxide slag |
| CN113501546A (en) * | 2021-04-30 | 2021-10-15 | 中南大学 | Method for synthesizing stable scorodite by simultaneously oxidizing and precipitating trivalent arsenic |
| CN115432802A (en) * | 2022-09-16 | 2022-12-06 | 大连理工大学 | A method for simultaneous removal of nitrite and arsenite pollution in groundwater |
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Cited By (3)
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| CN111573715A (en) * | 2020-06-16 | 2020-08-25 | 云南锡业研究院有限公司 | Method for preparing stannic oxide by using tin oxide slag |
| CN113501546A (en) * | 2021-04-30 | 2021-10-15 | 中南大学 | Method for synthesizing stable scorodite by simultaneously oxidizing and precipitating trivalent arsenic |
| CN115432802A (en) * | 2022-09-16 | 2022-12-06 | 大连理工大学 | A method for simultaneous removal of nitrite and arsenite pollution in groundwater |
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Application publication date: 20190416 |