CN108128880A - A kind of method for removing antimony in water removal using sulphite reinforcing manganese sand - Google Patents
A kind of method for removing antimony in water removal using sulphite reinforcing manganese sand Download PDFInfo
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- CN108128880A CN108128880A CN201711456386.7A CN201711456386A CN108128880A CN 108128880 A CN108128880 A CN 108128880A CN 201711456386 A CN201711456386 A CN 201711456386A CN 108128880 A CN108128880 A CN 108128880A
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- antimony
- sulphite
- manganese sand
- water
- removal
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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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- 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
- C02F2103/06—Contaminated groundwater or leachate
Abstract
It is a kind of to strengthen the method that manganese sand removes antimony in water removal using sulphite, be related to except antimony method, solve it is existing except antimony method medicament throwing amount is big, oxidant easily leaks, treatment technology is complicated, and use is inconvenient for operation, it is difficult to the problem of carrying out large-scale application.The method of the present invention：Add in sulphite into water containing antimony, introduce the water into the filter bed equipped with manganese sand, sulphite under the catalytic action of manganese sand, by oxygen rapid oxidation be potentiometric titrations, then, potentiometric titrations by adsorb manganese sand surface Sb3+It is oxidized to Sb5+, enhance removal of the manganese sand to antimony.Advantages of the present invention：Sulfite chemical property is stablized, and transport, storage are convenient, cheap, it is easy to operate, it does not need to additionally increase equipment, large-scale application can be carried out in water factory, manganese sand oxygen catalytic oxidation sulphite generation potentiometric titrations speed is fast, and potentiometric titrations can be rapidly by Sb3+It is oxidized to Sb5+, except antimony is efficient.
Description
Technical field
The present invention relates to drinking water treatment field more particularly to a kind of methods for removing antimony in drinking water.
Background technology
Antimony (Sb) is a kind of metalloid element for having metallic luster, is primarily present in the antimony-containing mineral of nature, such as brightness
Antimony ore, antimony bloom ore deposit.Since its thermal conductivity is not high, it is widely used in semiconducting alloy, battery, lubricant, ammunition, cable
The industrial circles such as foreskin, glass, welding alloy.China has become the antimony of maximum and its production of chemicals state in the world, and wherein
Most of tinnery for all originating from Lengshuijiang, Hunan again, but since production technique backwardness causes antimony pollution getting worse, tin
Soil, water body and vegetation around mine all receive serious pollution.Antimony can be enriched in organism and environment, and can be with
The sulfydryl of protein combines in cell, influences the activity of enzyme or destroy intracellular ion and balance to make cell hypoxia and cause human body generation
Thank to disorder.The antimony of human body continuous contact high concentration, can cause skin and mucous membrane to be stimulated, caused having of acute effects
Learn membranous conjunctivitis, rhinitis, pharyngitis, laryngitis, bronchitis, pneumonia；Antimony as the side effect of medicament include metabolic disorder and liver and
The degeneration of heart；Chronic Effect is including headache, dizzy, easy excitement, insomnia, weak, functions of intestines and stomach is disorderly, mucosal irritation symptom.
The concentration of antimony in Drinking Water has been done in certain limitation in toxicity and environmental safety based on antimony, China,《Drinking Water
Sanitary standard》(GB5749-2006) limit value of regulation antimony concentration is 5 μ g/L in.
In natural environment, antimony is mainly with trivalent antimony (Sb3+) and quinquevalence antimony (Sb5+) exist, the toxicity of trivalent antimony is pentavalent
10 times of antimony or more.At present, the method for removing antimony mainly has absorption method, coagulant sedimentation, oxidation-reduction method, ion-exchange etc..
Absorption method has many advantages, such as except antimony is efficient, easy to operate, but due to the interference of zwitterion in water, absorption method is to the dirt of low concentration antimony
The removal efficiency for contaminating object is relatively low.Coagulant sedimentation is mainly removed body pollution object by adding the co-precipitation of chemical agent coagulation
It removes, there are the problem of medicament throwing amount is big, and antimony removal efficiency is low.Oxidizing process is that trivalent antimony is oxidized to quinquevalence antimony, then passes through absorption
The mode of precipitation is removed.Patent CN103922512A discloses a kind of minimizing technology of micro-antimony in water, and ferrate will
Trivalent antimony is oxidized to quinquevalence antimony, while by the use of the nano-iron oxide for restoring generation as adsorbent, is adsorbed, precipitated, mistake
Elimination removes.(South China Normal University's journal, 2017,29 (3) such as Zhou Xueting：49-54) trivalent antimony is oxidized to using potassium ferrate
Then quinquevalence antimony utilizes the quinquevalence antimony in the ferric hydroxide colloid absorption water being formed in situ.Reduction method is to be reduced to quinquevalence antimony
Trivalent antimony.Patent CN103159300A discloses a kind of method that electrochemical method removes quinquevalence antimony pollutant in water removal, utilizes electricity
Quinquevalence antimony is reduced to trivalent antimony by chemical cathode, is then removed trivalent antimony by absorption, coagulation and precipitation collective effect.Patent
CN103408108A discloses the method that sodium sulfite quickly removes quinquevalence antimony pollutant in water removal with electrochemistry, utilizes anode
Dissolving method generates ferrous and iron ion, is combined with additional sodium sulfite, quinquevalence antimony is reduced to trivalent antimony, then pass through coagulation
With the trivalent antimony pollutant of precipitation removal generation.
In conclusion going the method for antimony in water removal at present, oxidant easily leaks, and treatment technology is multiple there are medicament throwing amount is big
Miscellaneous, use is inconvenient for operation, it is difficult to the problem of carrying out large-scale application.
Invention content
Except antimony method is there are medicament throwing amount is big, oxidant is easily leaked the purpose of the present invention is to solve existing, handles skill
Art is complicated, and use is inconvenient for operation, it is difficult to which the problem of carrying out large-scale application provides a kind of utilization sulphite and strengthen manganese sand
The method of antimony in water removal.
A kind of method for removing antimony in water removal using sulphite reinforcing manganese sand of the present invention, through the following steps that realizing
's：
First, sulphite is added in into accessing pending water containing antimony, control sulfite concentration is 5~100mg/L；
2nd, the accessing pending water containing sulphite is introduced into the filter bed equipped with manganese sand, after being filtered processing, that is, completed
The method for removing antimony in water removal using sulphite reinforcing manganese sand.
The accessing pending water is discharged for underground water or surface water after coagulation, precipitation process, and flow is shown in Fig. 1.
The sulphite is sodium sulfite (Na2SO3), potassium sulfite (K2SO3), calcium sulfite (CaSO3), bisulfite
Sodium (NaHSO3), potassium bisulfite (KHSO3) one or more of mixture.
A kind of principle that the method for antimony in water removal is gone using sulphite reinforcing manganese sand of the present invention：Water sulfite salt
(SO3 2-) under the catalytic action of manganese sand, by oxygen (O2) rapid oxidation be potentiometric titrations (SO4 ·-), see reaction equation (1) extremely
(3), then, the potentiometric titrations of generation can be rapidly by trivalent antimony (Sb of the absorption on manganese sand surface3+) oxidation generation be easy to
Quinquevalence antimony (the Sb of removal5+), see reaction equation (4), manganese sand is 5~10 times of trivalent antimony to the adsorption capacity of quinquevalence antimony, sulfurous acid
Salt enhances removal of the manganese sand to antimony in water, achievees the purpose that except antimony.
SO4 -+Sb3+→Sb5++SO4 2- (4)
A kind of method for removing antimony in water removal using sulphite reinforcing manganese sand of the present invention has the following advantages：
(1) sulfite chemical property is stablized, and transport, storage are convenient, cheap, are commercially easy to get；
(2) sulphite drinks water reducing agent catalogue by national be formally included in, easy to operate, does not need to additionally increase
Oil (gas) filling device does not change the original treatment process of water factory, can carry out large-scale application；
(3) it is fast to generate potentiometric titrations speed for manganese sand oxygen catalytic oxidation sulphite；
(4) potentiometric titrations can be rapidly by trivalent antimony (Sb3+) aoxidize the quinquevalence antimony (Sb that generation is easily removed5+), antimony
Removal efficiency is high, and removal rate is up to more than 96%.
Description of the drawings
Fig. 1 is a kind of technological process that the method for antimony in water removal is gone using sulphite reinforcing manganese sand.
Specific embodiment
Technical solution of the present invention is not limited to act specific embodiment set forth below, further includes between each specific embodiment
Arbitrary combination.
Specific embodiment one：A kind of method for removing antimony in water removal using sulphite reinforcing manganese sand of present embodiment,
Through the following steps that realize：
First, sulphite (SO is added in into accessing pending water containing antimony3 2-), control sulfite concentration is 5~100mg/L；
2nd, the accessing pending water containing sulphite is introduced into the filter bed equipped with manganese sand, after being filtered processing, that is, completed
The method for removing antimony in water removal using sulphite reinforcing manganese sand.
The accessing pending water is discharged for underground water or surface water after coagulation, precipitation process, and flow is shown in Fig. 1.
A kind of principle that the method for antimony in water removal is gone using sulphite reinforcing manganese sand of the present invention：Water sulfite salt
(SO3 2-) under the catalytic action of manganese sand, by oxygen (O2) rapid oxidation be potentiometric titrations (SO4 ·-), see reaction equation (1) extremely
(3), then, the potentiometric titrations of generation can be rapidly by trivalent antimony (Sb of the absorption on manganese sand surface3+) oxidation generation be easy to
Quinquevalence antimony (the Sb of removal5+), see reaction equation (4), manganese sand is 5~10 times of trivalent antimony to the adsorption capacity of quinquevalence antimony, sulfurous acid
Salt enhances removal of the manganese sand to antimony in water, achievees the purpose that except antimony.
SO4 ·-+Sb3+→Sb5++SO4 2- (4)
A kind of method for removing antimony in water removal using sulphite reinforcing manganese sand of the present invention has the following advantages：
(1) sulfite chemical property is stablized, and transport, storage are convenient, cheap, are commercially easy to get；
(2) sulphite drinks water reducing agent catalogue by national be formally included in, easy to operate, does not need to additionally increase
Oil (gas) filling device does not change the original treatment process of water factory, can carry out large-scale application；
(3) it is fast to generate potentiometric titrations speed for manganese sand oxygen catalytic oxidation sulphite；
(4) potentiometric titrations can be rapidly by trivalent antimony (Sb3+) aoxidize the quinquevalence antimony (Sb that generation is easily removed5+), antimony
Removal efficiency is high.
Specific embodiment two：The present embodiment is different from the first embodiment in that：In the accessing pending water
Sulfite concentration is 10~90mg/L.It is other same as the specific embodiment one.
Specific embodiment three：The present embodiment is different from the first and the second embodiment in that：The accessing pending water
In sulfite concentration be 15~80mg/L.It is other the same as one or two specific embodiments.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Described waits to locate
It is 20~70mg/L to manage the sulfite concentration in water.It is other identical with one of specific embodiment one to three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Described waits to locate
It is 30~60mg/L to manage the sulfite concentration in water.It is other identical with one of specific embodiment one to four.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：Described waits to locate
It is 40~50mg/L to manage the sulfite concentration in water.It is other identical with one of specific embodiment one to five.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Sulphite is
Sodium sulfite (Na2SO3), potassium sulfite (K2SO3), calcium sulfite (CaSO3), sodium hydrogensulfite (NaHSO3), potassium bisulfite
(KHSO3) one or more of mixture.Other steps and one of parameter and specific embodiment one to six are identical.
When present embodiment sulfite salt is mixture, with arbitrary than mixing.
Beneficial effects of the present invention are verified by following embodiment：
Embodiment 1：The present embodiment it is a kind of using sulphite strengthen manganese sand go water removal in antimony method, be by with
What lower step was realized：After coagulation, precipitation process, 20mg/L sulfurous acid is added in into water outlet for surface water containing 100 μ g/L antimony
Sodium (Na2SO3), manganese sand filter is introduced into, a concentration of 2 μ of remaining antimony in plasma mass spectrograph test water outlet is utilized after filtering
G/L, removal rate are less than up to 98%《Standards for drinking water quality》(GB5749-2006) limit of a concentration of 5 μ g/L of regulation antimony in
Value.
Embodiment 2：The present embodiment it is a kind of using sulphite strengthen manganese sand go water removal in antimony method, be by with
What lower step was realized：Underground water containing 50 μ g/L antimony adds in 20mg/L sodium hydrogensulfites (NaHSO into water outlet3), it is introduced into
Manganese sand filter, by a concentration of 1 μ g/L of remaining antimony in plasma mass spectrograph test water outlet after filtering, removal rate up to 98%,
It is less than《Standards for drinking water quality》(GB5749-2006) limit value of a concentration of 5 μ g/L of regulation antimony in.
Embodiment 3：The present embodiment it is a kind of using sulphite strengthen manganese sand go water removal in antimony method, be by with
What lower step was realized：After coagulation, precipitation process, 30mg/L sulfurous acid is added in into water outlet for surface water containing 100 μ g/L antimony
Potassium (K2SO3), manganese sand filter is introduced into, passes through a concentration of 2 μ of remaining antimony in plasma mass spectrograph test water outlet after filtering
G/L, removal rate are less than up to 98%《Standards for drinking water quality》(GB5749-2006) limit of a concentration of 5 μ g/L of regulation antimony in
Value.
Embodiment 4：The present embodiment it is a kind of using sulphite strengthen manganese sand go water removal in antimony method, be by with
What lower step was realized：After coagulation, precipitation process, 30mg/L sulfurous acid is added in into water outlet for surface water containing 100 μ g/L antimony
Calcium (CaSO3), manganese sand filter is introduced into, passes through a concentration of 3 μ of remaining antimony in plasma mass spectrograph test water outlet after filtering
G/L, removal rate are less than up to 97%《Standards for drinking water quality》(GB5749-2006) limit of a concentration of 5 μ g/L of regulation antimony in
Value.
Embodiment 5：The present embodiment it is a kind of using sulphite strengthen manganese sand go water removal in antimony method, be by with
What lower step was realized：Underground water containing 50 μ g/L antimony adds in 20mg/L potassium bisulfites (KHSO into water outlet3), it is introduced into
Manganese sand filter, by a concentration of 2 μ g/L of remaining antimony in plasma mass spectrograph test water outlet after filtering, removal rate up to 96%,
It is less than《Standards for drinking water quality》(GB5749-2006) limit value of a concentration of 5 μ g/L of regulation antimony in.
Embodiment 6：The present embodiment it is a kind of using sulphite strengthen manganese sand go water removal in antimony method, be by with
What lower step was realized：After coagulation, precipitation process, 60mg/L sulfurous acid is added in into water outlet for surface water containing 200 μ g/L antimony
Salt, sulphite are by potassium sulfite (K2SO3) and sodium sulfite (Na2SO3) it is 1 in molar ratio:1 ratio mixes, will
It introduces manganese sand filter, is reached after filtering by a concentration of 4 μ g/L of remaining antimony in plasma mass spectrograph test water outlet, removal rate
98%, it is less than《Standards for drinking water quality》(GB5749-2006) limit value of a concentration of 5 μ g/L of regulation antimony in.
Embodiment 7：The present embodiment it is a kind of using sulphite strengthen manganese sand go water removal in antimony method, be by with
What lower step was realized：After coagulation, precipitation process, 60mg/L sulfurous acid is added in into water outlet for surface water containing 200 μ g/L antimony
Salt, sulphite are by calcium sulfite (CaSO3) and sodium sulfite (Na2SO3) it is 1 in molar ratio:1 ratio mixes, will
It introduces manganese sand filter, is reached after filtering by a concentration of 4 μ g/L of remaining antimony in plasma mass spectrograph test water outlet, removal rate
98%, it is less than《Standards for drinking water quality》(GB5749-2006) limit value of a concentration of 5 μ g/L of regulation antimony in.
Embodiment 8：The present embodiment it is a kind of using sulphite strengthen manganese sand go water removal in antimony method, be by with
What lower step was realized：After coagulation, precipitation process, 60mg/L sulfurous acid is added in into water outlet for surface water containing 200 μ g/L antimony
Salt, sulphite are by sodium hydrogensulfite (NaHSO3) and sodium sulfite (Na2SO3) it is 1 in molar ratio:1 ratio mixing and
Into being introduced into manganese sand filter, by a concentration of 3 μ g/L of remaining antimony in plasma mass spectrograph test water outlet after filtering, go
Except rate is up to 98.5%, it is less than《Standards for drinking water quality》(GB5749-2006) limit value of a concentration of 5 μ g/L of regulation antimony in.
Embodiment 9：The present embodiment it is a kind of using sulphite strengthen manganese sand go water removal in antimony method, be by with
What lower step was realized：After coagulation, precipitation process, 60mg/L sulfurous acid is added in into water outlet for surface water containing 200 μ g/L antimony
Salt, sulphite are by potassium bisulfite (KHSO3) and sodium sulfite (Na2SO3) it is 1 in molar ratio:1 ratio mixes,
Manganese sand filter is introduced into, passes through a concentration of 4 μ g/L of remaining antimony in plasma mass spectrograph test water outlet, removal rate after filtering
Up to 98%, it is less than《Standards for drinking water quality》(GB5749-2006) limit value of a concentration of 5 μ g/L of regulation antimony in.
Embodiment 10：A kind of method for removing antimony in water removal using sulphite reinforcing manganese sand of the present embodiment, is to pass through
What following steps were realized：Underground water containing 100 μ g/L antimony adds in 50mg/L sulphite into water outlet, and sulphite is by Asia
Sodium sulphate (Na2SO3), potassium sulfite (K2SO3) and calcium sulfite (CaSO3) it is 1 in molar ratio:1:1 ratio mixes, will
It introduces manganese sand filter, is reached after filtering by a concentration of 3 μ g/L of remaining antimony in plasma mass spectrograph test water outlet, removal rate
97%, it is less than《Standards for drinking water quality》(GB5749-2006) limit value of a concentration of 5 μ g/L of regulation antimony in.
Embodiment 11：A kind of method for removing antimony in water removal using sulphite reinforcing manganese sand of the present embodiment, is to pass through
What following steps were realized：After coagulation, precipitation process, 80mg/L sulfurous is added in into water outlet for surface water containing 200 μ g/L antimony
Hydrochlorate, sulphite are by sodium sulfite (Na2SO3), potassium sulfite (K2SO3), calcium sulfite (CaSO3) and sodium hydrogensulfite
(NaHSO3) it is 1 in molar ratio:1:1:1 ratio mixes, and is introduced into manganese sand filter, passes through plasma constitution after filtering
A concentration of 3 μ g/L of remaining antimony, removal rate are less than up to 98.5% in spectrometer test water outlet《Standards for drinking water quality》
(GB5749-2006) limit value of a concentration of 5 μ g/L of regulation antimony in.
Embodiment 12：A kind of method for removing antimony in water removal using sulphite reinforcing manganese sand of the present embodiment, is to pass through
What following steps were realized：After coagulation, precipitation process, 80mg/L sulfurous is added in into water outlet for surface water containing 200 μ g/L antimony
Hydrochlorate, sulphite are by sodium sulfite (Na2SO3), potassium sulfite (K2SO3), calcium sulfite (CaSO3), sodium hydrogensulfite
(NaHSO3) and potassium bisulfite (KHSO3) it is 1 in molar ratio:1:1:1:1 ratio mixes, and is introduced into manganese sand filter,
It is less than after filtering by a concentration of 2 μ g/L of remaining antimony in plasma mass spectrograph test water outlet, removal rate up to 99%《Life
Sanitary standard for drinking water》(GB5749-2006) limit value of a concentration of 5 μ g/L of regulation antimony in.
It can be seen that strengthening manganese sand using sulphite goes the method for antimony in water removal with than more prominent advantage.
Claims (10)
- A kind of 1. method for removing antimony in water removal using sulphite reinforcing manganese sand, it is characterised in that it is through the following steps that realize 's：First, sulphite is added in into accessing pending water containing antimony, control sulfite concentration is 5~100mg/L；2nd, the accessing pending water containing sulphite is introduced into the filter bed equipped with manganese sand, after being filtered processing, that is, completes to utilize Sulphite strengthens the method that manganese sand removes antimony in water removal.
- 2. a kind of method for removing antimony in water removal using sulphite reinforcing manganese sand according to claim 1, it is characterised in that Sulphite is the mixed of one or more of sodium sulfite, potassium sulfite, calcium sulfite, sodium hydrogensulfite, potassium bisulfite Close object.
- 3. a kind of method for removing antimony in water removal using sulphite reinforcing manganese sand according to claim 1, it is characterised in that The accessing pending water is discharged for underground water or surface water after coagulation, precipitation process.
- 4. a kind of method for removing antimony in water removal using sulphite reinforcing manganese sand according to claim 1, it is characterised in that Sulfite concentration in the accessing pending water is 10~90mg/L.
- 5. a kind of method for removing antimony in water removal using sulphite reinforcing manganese sand according to claim 1, it is characterised in that Sulfite concentration in the accessing pending water is 15~80mg/L.
- 6. a kind of method for removing antimony in water removal using sulphite reinforcing manganese sand according to claim 1, it is characterised in that Sulfite concentration in the accessing pending water is 20~70mg/L.
- 7. a kind of method for removing antimony in water removal using sulphite reinforcing manganese sand according to claim 1, it is characterised in that Sulfite concentration in the accessing pending water is 30~60mg/L.
- 8. a kind of method for removing antimony in water removal using sulphite reinforcing manganese sand according to claim 1, it is characterised in that Sulfite concentration in the accessing pending water is 40~50mg/L.
- 9. a kind of method for removing antimony in water removal using sulphite reinforcing manganese sand according to claim 1, it is characterised in that Sulfite concentration in the accessing pending water is 35mg/L.
- 10. a kind of method for removing antimony in water removal using sulphite reinforcing manganese sand according to claim 1, it is characterised in that A concentration of 5~500 μ g/L of antimony in the accessing pending water.
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Cited By (1)
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| CN111707780A (en) * | 2020-07-03 | 2020-09-25 | 安徽盛世新能源材料科技有限公司 | Chemical detection method for content of antimony trioxide |
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