CN107188343A - Stibium-containing wastewater handling process - Google Patents
Stibium-containing wastewater handling process Download PDFInfo
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- CN107188343A CN107188343A CN201710647704.1A CN201710647704A CN107188343A CN 107188343 A CN107188343 A CN 107188343A CN 201710647704 A CN201710647704 A CN 201710647704A CN 107188343 A CN107188343 A CN 107188343A
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- waste water
- stibium
- containing wastewater
- chlorine dioxide
- treatment process
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- 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
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/763—Devices for the addition of such compounds in gaseous form
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to technical field of waste water processing, a kind of stibium-containing wastewater handling process is disclosed, including:Stibium-containing wastewater pH value by pretreatment is adjusted to 5.0~7.0;Waste water is sufficiently mixed with chlorine dioxide;The waste water for being mixed with chlorine dioxide is passed through triphase catalytic oxidation tower and occurs oxidation reaction;The waste water of gained is passed through and removes antimony reactor for treatment.After the stibium-containing wastewater handling process processing of the present invention, COD is significantly cut down in water, and with good biodegradability, so very big biochemistry pool need not be built, debugging cycle is also substantially shorter;By the waste water after biochemical treatment can qualified discharge, and pollutant can be made to drop to very low level completely, with good environmental effect.
Description
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of stibium-containing wastewater handling process.
Background technology
Antimony is a kind of non-renewable non-ferrous metal, antimony and its compound be widely used in ceramics, enamel, rubber, pigment,
The various fields such as semiconductor element, glass, alloy.However, antimony is not the indispensable element of organism, with accumulation toxicity and carcinogenic
Property, priority pollutants are classified as by American National Environmental Protection Administration (EPA) and European Union (EU).
Printing and dyeing industry is the essential industry of the coastal region in east China all the time.In fabrics printing and dyeing, polyester raw material polyester
When fiber is synthesized, in order to improve the conversion ratio of raw material, commonly using the catalyst containing antimony, such as antimony acetate, antimony glycol.So
And, in building-up process, antimony element can be evenly spread in polyester fiber with free state, these fibers enter printing and dyeing mill or
When weaving mill is processed further, in desizing and Alkali reduction process, free antimony will be entered in waste water and deposited.Layer
Layer accumulation after, in waste water the content of metallic antimony can more than 100 μ g/L, and《Textile dyeing and finishing industrial water pollution thing discharge standard》
(GB4287-2012) the limit value index for requiring metallic antimony is 100 μ g/L.Thus, the antimony being deposited in dyeing waste water how is removed
Just turning into printing and dyeing enterprise needs key problems-solving.
Less to the treatment research of stibium-containing wastewater both at home and abroad at present, main method has the precipitation method, electrochemical deposition method, cohesion
Method, microbial method and absorption method etc..Though these methods respectively have feature, all have some limitations, such as exist:Processing time
Long, cost is too high or secondary pollution problems.In consideration of it, the effectively processing of stibium-containing wastewater is extremely urgent, exploitation one kind was both passed through
Simple efficient stibium-containing wastewater handling process is shown Ji with solving above-mentioned professional problem present in current stibium-containing wastewater processing again
Obtain particularly important.
The content of the invention
The present invention is intended to provide a kind of not only economic but also simple efficient stibium-containing wastewater handling process.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of waste water treatment process, comprises the following steps:
S1, the stibium-containing wastewater pH value that will pass through pretreatment are adjusted to 5.0~7.0;
S2, the obtained waste water of step S1 and chlorine dioxide is sufficiently mixed;
S3, the waste water for being mixed with chlorine dioxide is passed through to triphase catalytic oxidation tower occurs oxidation reaction, the three-phase difference
For gas phase, liquid phase and solid phase, the gas phase is the compressed air that blower fan is sent into tower, and liquid phase is chlorine dioxide, and solid phase is fixation
Efficient composite catalyst on carrier;The efficient composite catalyst is noble metal or transistion metal compound, the carrier
For Fe carriers;
S4, by the S3 gained waste water pass through remove antimony reactor for treatment.
Preferably, the chlorine dioxide is prepared by chlorine dioxide generator, useless containing antimony into catalytic oxidizing equipment
Chlorine dioxide and COD in pending stibium-containing wastewater mass ratio are 6~9 in water:1.
Preferably, the volume ratio of stibium-containing wastewater of the intake of the compressed air with entering catalytic oxidizing equipment is 50
~80:1.
Preferably, the time of the oxidation reaction is 10~30min.
Preferably, the efficient composite catalyst by weight percentage, is consisted of the following composition:
Preferably, the preparation method of the efficient composite catalyst includes:
The component of the efficient composite catalyst is equipped to add Fe carriers after maceration extract and is well mixed.
Preferably, the Fe carriers and maceration extract weight ratio are 1.0~1.5:1.
Preferably, the preparation method of the efficient composite catalyst is also included well mixed support-activated, activation
Temperature is 500~580 DEG C, and the time is 2~4h.
Preferably, above-mentioned stibium-containing wastewater handling process also includes the waste water progress biochemical treatment after being handled except antimony.
Technical scheme, has the following advantages that:
1. chlorine dioxide strong oxidizer is employed in the stibium-containing wastewater technique of the present invention, i.e., first through two before catalysis oxidation
Appropriate air is passed through after oxidation oxychloride in catalysis oxidizing tower again to be catalyzed with waste water and the high efficiency composition being fixed on carrier
Agent constitutes triphase catalytic oxidation situation.The stibium-containing wastewater technique core of the present invention is " triphase catalytic oxidation technology ", and its principle is just
It is under conditions of surface catalyst presence, to utilize strong oxidizer --- chlorine dioxide is at normal temperatures and pressures in catalysis oxidation waste water
Organic pollution, or direct oxidation organic pollution, or macromolecular organic pollution is oxidized to small molecule organic pollution,
Preferably removal organic polluter is removed while interrupting the double bond chromophore (such as azo group, nitro, vulcanization hydroxyl) in organic molecule,
The colourity of waste water is removed well.The use of the composite catalyst, makes the oxygen in air also with chlorine dioxide equally conduct
Oxidant participates in reaction, so as to reduce the consumption of Oxygen in Liquid agent chlorine dioxide, reduces the cost of processing, improves processing
Efficiency, while also greatly improving reaction speed, shortens residence time of the waste water in triphase catalytic oxidation tower.
2. the present invention efficient composite catalyst filling carrier be iron, on the basis of iron incorporate copper, nickel, manganese, platinum, ruthenium,
Niobium, palladium etc. more than ten plants noble metal and its compound, and ferrous ion and other transition metal, noble metal member are utilized during the course of the reaction
Plain concerted reaction, substantially increases the efficiency of catalysis oxidation, reduces the consumption of oxidant, reduces the cost of processing;In addition,
Iron continuous solution modeling in acid condition, gained molysite belongs to excellent flocculant, can reduce the chemical feeding quantity of later stage flocculant,
Simultaneously because what is added is sour limited, so reaction is automatically stopped after acid and complete iron reaction, without causing excessive iron
Elemental release, so as to reduce the amount of sludge generation.
3. the efficient composite catalyst preparation method of the present invention is simple, the reaction time is short, and service life is long, and turnover rate is low,
Raw material is easy to get, and prepares cost low.
4. the stibium-containing wastewater handling process of the present invention is simple, it can be completed using the reactor of Fenton process, automaticity
Height, equipment investment is few.
5. after the stibium-containing wastewater handling process processing for passing through the present invention, COD is significantly cut down in water, and can with good
Biochemical, so very big biochemistry pool need not be built, debugging cycle is also substantially shorter;Can be complete by the waste water after biochemical treatment
Qualified discharge, and pollutant can be made to drop to very low level, with good environmental effect.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The accompanying drawing used required in embodiment or description of the prior art is briefly described, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the schematic flow sheet of stibium-containing wastewater handling process of the present invention;
Fig. 2 is that the present invention removes antimony structure of reactor schematic diagram;
Fig. 3 is the front view of porous plate of the present invention.
Reference:
1- venting channels;2- water flowing passages;3- porous plates;4- packing layers.
Embodiment
Technical scheme will be clearly and completely described below, it is clear that described embodiment is this hair
Bright a part of embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not having
There is the every other embodiment made and obtained under the premise of creative work, belong to the scope of protection of the invention.In addition, below
Just can be mutual as long as the technical characteristic involved by described different embodiments of the present invention does not constitute conflict each other
With reference to.
Embodiment 1
As shown in figure 1, the stibium-containing wastewater by pretreatment, which enters pH, adjusts pond, its pH value is adjusted to 5.0~6.0, led to
Pump pump is crossed to filter, the suspension in waste water is removed, prevents from polluting and blocks efficiently urging in follow-up triphase catalytic oxidation tower
Agent.Filter water outlet enters cyclic absorption tank, the chlorine dioxide that cyclic absorption tank constantly produces chlorine dioxide generator
It is mixed into stibium-containing wastewater, and enter in triphase catalytic oxidation tower after being sufficiently mixed in cyclic absorption tank.In three-phase catalytic
In the presence of effective catalyst in oxidizing tower, the oxygen in chlorine dioxide and compressed air is removed in waste water by oxidation reaction
Hardly degraded organic substance, the COD in waste water is reduced, while being stripped of the colourity of waste water.Waste water warp after catalytic oxidation treatment
Except antimony, biochemical treatment, COD is stable in below 40mg/L, and antimony content is low to 14 μ g/L or so, can be emitted into outer shroud with stably reaching standard
Border.
In the present embodiment, chlorine dioxide and COD in pending stibium-containing wastewater mass ratio are 7.5 in stibium-containing wastewater:1, institute
The volume ratio for stating stibium-containing wastewater of the intake of compressed air with entering catalytic oxidizing equipment is 50:1, the oxidation reaction when
Between be 10min.
In the present embodiment, the three-phase is respectively gas phase, liquid phase and solid phase, and the gas phase is the compression that blower fan is sent into tower
Air, liquid phase is chlorine dioxide, and solid phase is the efficient composite catalyst being fixed on carrier;The efficient composite catalyst is expensive
Metal or transistion metal compound, the carrier are Fe carriers.
Wherein, the content of the efficient composite catalyst each component is respectively:Palladium 0.7g, ruthenium 0.4g, iridium 0.2g, osmium
0.3g, manganese 2.7g, copper 1.5g, aluminium 1.0g, iron 93.2g.
The preparation method of the efficient composite catalyst is:Above-mentioned each group is distributed into after maceration extract and adds Fe carriers and mixes
Close uniform, then by resulting vehicle in 520~550 DEG C of activation 3h, wherein:The Fe carriers are 1.2 with maceration extract weight ratio:1.
It is described multiple except being distributed on antimony reactor except antimony processing using as shown in Figure 2 except antimony reactor in the present embodiment
Porous plate and packing layer as shown in Figure 3.
Embodiment 2
As shown in figure 1, the stibium-containing wastewater by pretreatment, which enters pH, adjusts pond, its pH value is adjusted to 5.5~6.5, led to
Pump pump is crossed to filter, the suspension in waste water is removed, prevents from polluting and blocks efficiently urging in follow-up triphase catalytic oxidation tower
Agent.Filter water outlet enters cyclic absorption tank, the chlorine dioxide that cyclic absorption tank constantly produces chlorine dioxide generator
It is mixed into stibium-containing wastewater, and enter in triphase catalytic oxidation tower after being sufficiently mixed in cyclic absorption tank.In three-phase catalytic
In the presence of effective catalyst in oxidizing tower, the oxygen in chlorine dioxide and compressed air is removed in waste water by oxidation reaction
Hardly degraded organic substance, the COD in waste water is reduced, while being stripped of the colourity of waste water.Waste water warp after catalytic oxidation treatment
Except antimony, biochemical treatment, COD is stable in below 45mg/L, and antimony content is low to 18 μ g/L or so, can be emitted into outer shroud with stably reaching standard
Border.
In the present embodiment, chlorine dioxide and COD in pending stibium-containing wastewater mass ratio are 6 in stibium-containing wastewater:1, it is described
The volume ratio of stibium-containing wastewater of the intake of compressed air with entering catalytic oxidizing equipment is 60:1, the time of the oxidation reaction
For 15min.
In the present embodiment, the three-phase is respectively gas phase, liquid phase and solid phase, and the gas phase is the compression that blower fan is sent into tower
Air, liquid phase is chlorine dioxide, and solid phase is the efficient composite catalyst being fixed on carrier;The efficient composite catalyst is expensive
Metal or transistion metal compound, the carrier are Fe carriers.
Wherein, the content of the efficient composite catalyst each component is respectively:Palladium 0.5g, ruthenium 0.2g, iridium 0.1g, osmium
0.2g, manganese 2.4g, copper 1.0g, aluminium 0.5g, iron 95.1g.
The preparation method of the efficient composite catalyst is:Above-mentioned each group is distributed into after maceration extract and adds Fe carriers and mixes
Close uniform, then by resulting vehicle in 500~520 DEG C of activation 4h, wherein:The Fe carriers are 1.5 with maceration extract weight ratio:1.
It is described multiple except being distributed on antimony reactor except antimony processing using as shown in Figure 2 except antimony reactor in the present embodiment
Porous plate and packing layer as shown in Figure 3.
Embodiment 3
As shown in figure 1, the stibium-containing wastewater by pretreatment, which enters pH, adjusts pond, its pH value is adjusted to 6.0~7.0, led to
Pump pump is crossed to filter, the suspension in waste water is removed, prevents from polluting and blocks efficiently urging in follow-up triphase catalytic oxidation tower
Agent.Filter water outlet enters cyclic absorption tank, the chlorine dioxide that cyclic absorption tank constantly produces chlorine dioxide generator
It is mixed into stibium-containing wastewater, and enter in triphase catalytic oxidation tower after being sufficiently mixed in cyclic absorption tank.In three-phase catalytic
In the presence of effective catalyst in oxidizing tower, the oxygen in chlorine dioxide and compressed air is removed in waste water by oxidation reaction
Hardly degraded organic substance, the COD in waste water is reduced, while being stripped of the colourity of waste water.Waste water warp after catalytic oxidation treatment
Except antimony, biochemical treatment, COD is stable in below 50mg/L, and antimony content is low to 16 μ g/L or so, can be emitted into outer shroud with stably reaching standard
Border.
In the present embodiment, chlorine dioxide and COD in pending stibium-containing wastewater mass ratio are 9 in stibium-containing wastewater:1, it is described
The volume ratio of stibium-containing wastewater of the intake of compressed air with entering catalytic oxidizing equipment is 80:1, the time of the oxidation reaction
For 30min.
In the present embodiment, the three-phase is respectively gas phase, liquid phase and solid phase, and the gas phase is the compression that blower fan is sent into tower
Air, liquid phase is chlorine dioxide, and solid phase is the efficient composite catalyst being fixed on carrier;The efficient composite catalyst is expensive
Metal or transistion metal compound, the carrier are Fe carriers.
Wherein, the content of the efficient composite catalyst each component is respectively:Palladium 1.0g, ruthenium 0.6g, iridium 0.3g, osmium
0.4g, manganese 3.0g, copper 2.0g, aluminium 1.5g, iron 91.2g.
The preparation method of the efficient composite catalyst is:Above-mentioned each group is distributed into after maceration extract and adds Fe carriers and mixes
Close uniform, then by resulting vehicle in 560~580 DEG C of activation 2h, wherein:The Fe carriers are 1.0 with maceration extract weight ratio:1.
It is described multiple except being distributed on antimony reactor except antimony processing using as shown in Figure 2 except antimony reactor in the present embodiment
Porous plate and packing layer as shown in Figure 3.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments, and the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (9)
1. a kind of waste water treatment process, it is characterised in that comprise the following steps:
S1, the stibium-containing wastewater pH value that will pass through pretreatment are adjusted to 5.0~7.0;
S2, the obtained waste water of step S1 and chlorine dioxide is sufficiently mixed;
S3, the waste water for being mixed with chlorine dioxide is passed through to triphase catalytic oxidation tower occurs oxidation reaction, the three-phase is respectively gas
Phase, liquid phase and solid phase, the gas phase are the compressed air that blower fan is sent into tower, and liquid phase is chlorine dioxide, and solid phase is to be fixed on load
Efficient composite catalyst on body;The efficient composite catalyst is noble metal or transistion metal compound, and the carrier is Fe
Carrier;
S4, by the S3 gained waste water pass through remove antimony reactor for treatment.
2. waste water treatment process according to claim 1, it is characterised in that the chlorine dioxide occurs by chlorine dioxide
It is prepared by device, into the stibium-containing wastewater of catalytic oxidizing equipment in chlorine dioxide and pending stibium-containing wastewater COD mass ratio for 6~
9:1。
3. waste water treatment process according to claim 2, it is characterised in that the intake of the compressed air is urged with entering
The volume ratio for changing the stibium-containing wastewater of oxidation unit is 50~80:1.
4. waste water treatment process according to claim 1, it is characterised in that the time of the oxidation reaction is 10~
30min。
5. the waste water treatment process according to claim any one of 1-4, it is characterised in that the efficient composite catalyst is pressed
Percentage by weight meter, is consisted of the following composition:
6. waste water treatment process according to claim 5, it is characterised in that the preparation method of the efficient composite catalyst
Including:
The component of the efficient composite catalyst is equipped to add Fe carriers after maceration extract and is well mixed.
7. waste water treatment process according to claim 6, it is characterised in that the Fe carriers are with maceration extract weight ratio
1.0~1.5:1.
8. the waste water treatment process according to claim 6 or 7, it is characterised in that the preparation of the efficient composite catalyst
Method also includes will be well mixed support-activated, and activation temperature is 500~580 DEG C, and the time is 2~4h.
9. the waste water treatment process according to claim any one of 1-8, it is characterised in that also including will be after being handled except antimony
Waste water carry out biochemical treatment.
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Cited By (1)
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CN114605010A (en) * | 2022-03-23 | 2022-06-10 | 清莱环境科技(上海)有限公司 | Method for removing antimony from printing and dyeing wastewater |
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