CN108996656A - A kind of method that thermal activation sodium peroxydisulfate removes coal chemical industrial waste water COD with high salt - Google Patents
A kind of method that thermal activation sodium peroxydisulfate removes coal chemical industrial waste water COD with high salt Download PDFInfo
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- CN108996656A CN108996656A CN201810939397.9A CN201810939397A CN108996656A CN 108996656 A CN108996656 A CN 108996656A CN 201810939397 A CN201810939397 A CN 201810939397A CN 108996656 A CN108996656 A CN 108996656A
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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
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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
- C02F2101/30—Organic 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Environmental & Geological Engineering (AREA)
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Abstract
The present invention is a kind of method that thermal activation persulfate removes coal chemical industrial waste water COD with high salt.This method comprises the following steps: 1) persulfate is added into the reactor for fill coal chemical industrial waste water, additional amount is that 10-30 g persulfate is added in every liter of coal chemical industrial waste water；2) H is used2SO4Or the pH value of waste water walked in NaOH adjusting is 11.5-12.5, then at 75 ~ 85 DEG C after isothermal reaction 3-6 h, completes the degradation to coal chemical industrial waste water；Waste water COD to be processed is 300-1300 mg/L in the step 1), and chlorine ion concentration is 3500-30000 mg/L, and TDS range is 7000-77000 mg/L.The present invention can aoxidize hardly degraded organic substance in high-salt wastewater, reach the COD removal rate of 60-85%, and by-product is Na contained by coal chemical industrial waste water itself2SO4, the introducing without other pollutants.
Description
Technical field
The invention belongs to advanced treatment of industrial waste water field, in particular to a kind of thermal activation persulfate removes coalification with high salt
The method of work waste water COD.
Background technique
In recent years, with the fast development of national economy, the high-concentration waste water generated in industrial processes, to water
Resource causes harm.Coal chemical industry using coal as raw material, by chemical conversion make coal be converted into gas, liquid and solid fuel and
Other chemicals.But a large amount of waste water generated during coal chemical industry have COD, and (Chemical Oxygen Demand, chemistry need
Oxygen amount) value height, the feature that salt content is high, coloration is deep, hard-degraded substance is more, belong to high concentration hard-degraded organic waste water, tradition
Processing method such as biochemical treatment is difficult to realize that such waste water is effectively treated.
For coal chemical industrial waste water on the basis of preceding processing, the concentrated water after reverse osmosis treatment or further electrodialysis process has height
The characteristics of salt content, high Cl- concentration, contains part hardly degraded organic substance simultaneously.Such waste water leads to not because of high salinity
It is directly entered biochemical system processing, contained hardly degraded organic substance can bring tired to the operation of the processing means such as rear end evaporative crystallization
It is difficult.Therefore, it is in urgent need for the high-efficient treatment method of this kind of waste water.
Advanced oxidation processes (Advanced Oxidation Process, AOP) are fast with reaction speed, processing is complete,
The advantages that applied widely.Oxidation operation can be degraded into small-molecule substance by the strong oxidizing property free radical that the technique generates, very
To being ultimately oxidized as water (H2) and carbon dioxide (CO O2).But it is traditional with hydroxyl radical free radical (OH) be main active substances
AOP technology there are oxidabilities limited, higher cost, secondary pollution problems, and the processing to the high salt waste water of coal chemical industry
Effect is undesirable.
In recent years, emerging activation persulfate (persulfate, PS) high-level oxidation technology causes the wide of scholars
General concern.Since its oxidation mechanism is considered to depend on potentiometric titrations (SO more4 -), and unconventional OH, because of this person
The technology is known as advanced oxidation technology.Activate what persulfate high-level oxidation technology was generated using activation persulfate
Potentiometric titrations oxidative degradation organic matter, product SO4 2-, for itself containing a large amount of Na2SO4It is with high salt with the coal chemical industry of NaCl
Waste water does not constitute new secondary pollution, is a kind of ideal processing method.Potentiometric titrations oxidability is near or above hydroxyl
Base free radical (SO4 -Oxidation-reduction potential E0The oxidation-reduction potential E of=2.5-3.1V, OH0=1.89-2.72V), and
SO4 -Stability be more than OH (SO that traditional advanced oxidation processes generate4 -Half-life period is 40 μ s, the half of considerably longer than OH
Decline the phase (< 1 μ s)), it is bigger with the haptoreaction chance of pollutant.In addition, the stability under persulfate good water solubility, room temperature
Product is mild after high, cheap, reaction.Therefore, the high-level oxidation technology of persulfate is activated in wastewater treatment, especially coal
It has a extensive future in the application of wastewater from chemical industry advanced treating.
There are many activating means for persulfate, typical such as thermal activation, alkali activation, UV activation, transition metal activation
Deng.There are equipment corrosion for alkali activation；Coal chemical industrial waste water higher for coloration, UV activation effect are poor；Transition metal is living
There is secondary pollution and metal quencher in change.
Rarely have in recent years and thermal activation persulfate high-level oxidation technology is used for COD in actual coal chemical industrial waste water with high salt
Removal research or application.
Summary of the invention
It is an object of the invention to it is high to provide a kind of thermal activation persulfate removal for deficiency present in current techniques
The method of COD in salt coal chemical industrial waste water, this method, as oxidant, are generated freely using sodium peroxydisulfate by thermal activation (heating)
Base is aoxidized, and is adjusted the simple process that pH is alkalinity by addition acid or alkali on this basis and is made the oxidizing process to previous living
Change the reluctant high salinity and chlorine organic wastewater of persulfate and reach better removal effect, with high salt, high-chlorine coal chemical industry can be solved
The difficult problem of waste water hardly degraded organic substance COD removal.The present invention can aoxidize hardly degraded organic substance in high-salt wastewater, reach 60-
85% COD removal rate, and by-product is the Na that coal chemical industrial waste water itself just contains2SO4, the introducing without other pollutants.
The technical solution of the present invention is as follows:
A kind of method that thermal activation persulfate removes coal chemical industrial waste water COD with high salt, which is characterized in that including walking as follows
It is rapid:
1) persulfate is added into the reactor for fill coal chemical industrial waste water, additional amount is to be added in every liter of coal chemical industrial waste water
10-30g persulfate；
2) H is used2SO4Or the pH value of waste water walked in NaOH adjusting is 11.5-12.5, the then constant temperature at 75~85 DEG C
After reacting 3-6h, the degradation to coal chemical industrial waste water is completed；
Waste water COD to be processed is 300-1300mg/L, chlorine ion concentration 3500-30000mg/L in the step 1),
TDS range is 7000-77000mg/L.
Persulfate is sodium peroxydisulfate in the step 1).
The method of the present invention has the beneficial effect that
(1) the method for the present invention is based on potentiometric titrations oxidation mechanisms, passes through thermal activation Na2S2O8Generate strong oxidizing property certainly
By base SO4 -, conventional treatment method is compared, (or part removes) hardly degraded organic substance, and synchronous reduction waste water COD can be removed
Value.
(2) the method for the present invention is based on potentiometric titrations oxidation mechanisms, can overcome coal chemical industrial waste water hypersaline environment, not by useless
The influence of a large amount of inorganic ions in water.
(3) the persulfate good water solubility that the method for the present invention is selected, energy storage-stable, relative low price, and after reaction
By-product is Na2SO4, introducing without secondary pollution is subsequent to evaporate salt manufacturing recycling.
(4) the method for the present invention generates strong oxidizing property free radical using thermal activation persulfate, solves fragrant in the prior art
Oxidation oxidability of pausing is poor；There are equipment corrosion for alkali activation；Coal chemical industrial waste water higher for coloration, UV activation effect compared with
Difference；There are secondary pollutions and metal ion, and the technical problems such as free radical are quenched for transition metal activation.
(5) present invention combines the convenience of a variety of UTILIZATION OF VESIDUAL HEAT INs of coal chemical industry, obtains sulfate radical certainly by thermal activation persulfate
It is an appropriate energy-saving and emission-reduction approach by base, and thermal activation can also increase the solvability of slightly soluble organic matter, strengthen reaction speed
Rate and mineralising efficiency can reach the COD removal rate of 60-85%, significant effect.
Specific embodiment
Below with reference to the method that embodiment removes coal chemical industrial waste water COD with high salt to thermal activation persulfate, carry out specifically
It is bright.It should be understood that these embodiments are merely to illustrate the present invention, rather than limit the scope of the invention.
Waste water to be processed of the present invention is that certain the large-scale coal chemical industry of coal chemical industry enterprises containing persistent organic pollutants is useless
Water, or the concentrated water after preprocessed, biochemical treatment, reverse osmosis treatment or be concentrated on its basis through further electrodialysis dense
Water.Wherein, persistent organic pollutants are mainly one of benzene, biphenyl, volatile phenol, ketone, naphthalene, pyridine and carbazole or more
Kind.
Embodiment 1
(1) it takes the 100mL waste water (condensed water) that COD is 1300 in reactor, 3g sodium peroxydisulfate is added, makes mistake in solution
Sodium sulfate concentration is that (solution is neutral to 30g/L at this time, and pH is about that 7), adjusting the initial pH of waste water with NaOH is 11.5~12.5.
(2) reactor is put into 80 ± 2 DEG C of thermostat water baths (heated at constant temperature is provided by coal chemical industry Low Temperature Steam), makes its liter
Temperature starts potentiometric titrations oxidation reaction, reaction time 3h to 80 DEG C.
(3) reactor in step (2) after reaction is taken out, is rapidly cooled to room temperature using water-bath, terminates reaction,
Solution is to react water outlet in reactor.Wherein, sodium sulphate is converted into after sodium peroxydisulfate degradation of organic substances, sodium sulphate is former useless
Have component in water, therefore new pollutant will not be introduced in system, and subsequent can be produced by dividing salt crystallization to obtain sodium sulphate respectively
Product and sodium chloride product.
(4) to reaction water outlet in step (3) according to People's Republic of China's environmental protection professional standard HJ/T70-2001 into
The measurement of row COD, and TDS is measured using TDS detection pen, it the results are shown in Table 1.
Embodiment 2
For other steps with embodiment 1, difference is that processing waste water is changed to not concentrated fresh water (COD 350-
400mg/L), and using 1g sodium peroxydisulfate the 3g sodium peroxydisulfate in step (1) is replaced, experimental result is shown in Table 1.
Step (3), (4) reaction water outlet COD and TDS measurement result in 1 embodiment 1,2 of table
Embodiment 3
Industrial wastewater in the present embodiment is derived from certain large-scale coal chemical industry after preprocessed, biochemical treatment, reverse osmosis treatment
Reverse osmosis (Reverse Osmosis, the RO) concentrated water and electrodialysis (Electrodialysis, ED) fresh water of enterprise wastewater, specifically
Implementation steps are as follows:
(1) it takes the 100mL waste water (RO concentrated water) that COD is 700mg/L in reactor, 1g sodium peroxydisulfate is added, makes solution
Middle sodium peroxydisulfate concentration is 10g/L, is 11.5~12.5 with the initial pH that NaOH adjusts waste water.
(2) reactor is put into 80 ± 2 DEG C of thermostat water baths, so that it is warming up to 80 DEG C, starting potentiometric titrations oxidation
Reaction, reaction time 3h.
(3) reactor in step (2) after reaction is taken out, is rapidly cooled to room temperature using water-bath, terminates reaction,
Solution is to react water outlet in reactor.
(4) to reaction water outlet in step (3) according to People's Republic of China's environmental protection professional standard HJ/T70-2001 into
The measurement of row COD, and TDS is measured using TDS detection pen, it the results are shown in Table 2.
Comparative example 1:
To prove that the present invention carries out the degradation capability of hardly degraded organic substance in coal chemical industrial waste water for embodiment 3 simultaneously
It is not added with the comparison (i.e. for other steps with embodiment 3, difference is not add sodium peroxydisulfate) of persulfate oxidation agent.
The result shows that COD value is without significant change after being not added with the waste water reaction of persulfate.
Embodiment 4
Other steps are with embodiment 3, and difference is that will handle waste water to be changed to ED fresh water (COD 636mg/L), experiment knot
Fruit is shown in Table 2.
Step (3), (4) reaction water outlet COD and TDS measurement result in 2 embodiment 3,4 of table
In conclusion high chlorine, coal chemical industrial waste water with high salt can be effectively treated in method of the invention, reach preferable COD removal
Effect (60-85%).Therefore the present invention it is a kind of activation persulfate removal coal chemical industry high-salt wastewater COD method for high chlorine,
Coal chemical industrial waste water with high salt has the extensive scope of application and wide application prospect.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection scope of technical solution of the present invention.
Unaccomplished matter of the present invention is well-known technique.
Claims (2)
1. a kind of method that thermal activation persulfate removes coal chemical industrial waste water COD with high salt, it is characterised in that include the following steps:
1) persulfate is added into the reactor for fill coal chemical industrial waste water, additional amount is that 10- is added in every liter of coal chemical industrial waste water
30 g persulfates；
2) H is used2SO4Or the pH value of waste water walked in NaOH adjusting is 11.5-12.5, the then isothermal reaction at 75 ~ 85 DEG C
After 3-6 h, the degradation to coal chemical industrial waste water is completed；
Waste water COD to be processed is 300-1300 mg/L in the step 1), and chlorine ion concentration is 3500-30000 mg/L, TDS
Range is 7000-77000 mg/L.
2. the method that thermal activation persulfate as described in claim 1 removes coal chemical industrial waste water COD with high salt, it is characterised in that institute
Stating persulfate in step 1) is sodium peroxydisulfate.
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Cited By (10)
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|---|---|---|---|---|
| CN110104758A (en) * | 2019-06-19 | 2019-08-09 | 河北工业大学 | A kind of method that electricity cooperates with organic matter in persulfate advanced treating high-salt wastewater |
| CN110255696A (en) * | 2019-07-23 | 2019-09-20 | 大连民族大学 | A kind of system using remaining alkali Heat Treatment purified cotton black liquor |
| CN110407308A (en) * | 2019-07-16 | 2019-11-05 | 武汉理工大学 | A kind of method of nano zero valence iron collaboration thermal activation persulfate chloramphenicol degrading |
| CN110759578A (en) * | 2019-11-04 | 2020-02-07 | 神美科技有限公司 | Treatment method of coal chemical industry washing wastewater |
| CN111018230A (en) * | 2020-01-14 | 2020-04-17 | 北京赛科康仑环保科技有限公司 | Method for realizing zero discharge and resource utilization of reverse osmosis concentrated water in coal chemical industry |
| CN111875026A (en) * | 2020-06-19 | 2020-11-03 | 广西大学 | thermo-Na2S2O8Method for deeply treating pulping and papermaking wastewater by system |
| CN113087121A (en) * | 2021-05-11 | 2021-07-09 | 华东理工大学 | Method for degrading pyrazine in acetylpyrazine production wastewater |
| CN114163061A (en) * | 2022-02-14 | 2022-03-11 | 浙江浙能技术研究院有限公司 | Method for efficiently degrading organic matters in wastewater by virtue of hydrothermal persulfate catalytic oxidation |
| CN114477412A (en) * | 2020-10-26 | 2022-05-13 | 华中科技大学 | Method for removing organic pollutants in water by thermally activating persulfate |
| CN114920347A (en) * | 2022-06-08 | 2022-08-19 | 河海大学 | Organic dye industrial wastewater degradation agent and degradation process |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110104758A (en) * | 2019-06-19 | 2019-08-09 | 河北工业大学 | A kind of method that electricity cooperates with organic matter in persulfate advanced treating high-salt wastewater |
| CN110104758B (en) * | 2019-06-19 | 2022-05-06 | 河北工业大学 | Method for deeply treating organic matters in high-salinity wastewater by virtue of electric cooperation with persulfate |
| CN110407308A (en) * | 2019-07-16 | 2019-11-05 | 武汉理工大学 | A kind of method of nano zero valence iron collaboration thermal activation persulfate chloramphenicol degrading |
| CN110255696A (en) * | 2019-07-23 | 2019-09-20 | 大连民族大学 | A kind of system using remaining alkali Heat Treatment purified cotton black liquor |
| CN110759578B (en) * | 2019-11-04 | 2022-05-03 | 神美科技有限公司 | Treatment method of coal chemical industry washing wastewater |
| CN110759578A (en) * | 2019-11-04 | 2020-02-07 | 神美科技有限公司 | Treatment method of coal chemical industry washing wastewater |
| CN111018230B (en) * | 2020-01-14 | 2022-04-12 | 北京赛科康仑环保科技有限公司 | Method for realizing zero discharge and resource utilization of reverse osmosis concentrated water in coal chemical industry |
| CN111018230A (en) * | 2020-01-14 | 2020-04-17 | 北京赛科康仑环保科技有限公司 | Method for realizing zero discharge and resource utilization of reverse osmosis concentrated water in coal chemical industry |
| CN111875026A (en) * | 2020-06-19 | 2020-11-03 | 广西大学 | thermo-Na2S2O8Method for deeply treating pulping and papermaking wastewater by system |
| CN114477412A (en) * | 2020-10-26 | 2022-05-13 | 华中科技大学 | Method for removing organic pollutants in water by thermally activating persulfate |
| CN113087121A (en) * | 2021-05-11 | 2021-07-09 | 华东理工大学 | Method for degrading pyrazine in acetylpyrazine production wastewater |
| CN114163061A (en) * | 2022-02-14 | 2022-03-11 | 浙江浙能技术研究院有限公司 | Method for efficiently degrading organic matters in wastewater by virtue of hydrothermal persulfate catalytic oxidation |
| CN114920347A (en) * | 2022-06-08 | 2022-08-19 | 河海大学 | Organic dye industrial wastewater degradation agent and degradation process |
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