CN106630262B - Method for effectively removing organic matters in high-salt water zero-discharge process - Google Patents
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Abstract
The invention provides a method for effectively removing organic matters in a high-saline water zero-discharge process, which comprises the following steps of: oxidizing the homogenized wastewater in an oxidation pond; introducing the wastewater after oxidation treatment into a coagulation tank for coagulation; introducing the wastewater subjected to coagulation treatment into an adsorption tank, and adding an adsorbent for adsorption; and carrying out solid-liquid separation on the wastewater after the adsorption treatment. Through the integration of several technologies, the effective removal of organic matters is realized, and the removal rate of COD can reach 70-80%. By technical integration, synergy is achieved, and processing cost is reduced 1/4.
Description
Technical Field
The embodiment of the invention relates to a method for effectively removing organic matters in a high-saline water zero-emission process.
Background
In recent years, the coal chemical industry has been rapidly developed. However, as the coal chemical industry needs to consume a large amount of water, the problems of water resource recycling and environmental protection are increasingly prominent, and the northwest inland areas with much drought and little rain are particularly prominent. However, no matter the membrane method, the thermal method or the ion exchange method is adopted to prepare desalted water, the byproduct of the salt-containing wastewater is inevitable.
The salt in the high-salt water in the coal chemical industry mainly comes from circulating water, strong brine generated by carrying and concentrating in the preparation process of desalted water and adding various medicaments in the process of treating and recycling industrial wastewater. The high-salt water in the coal chemical industry generally shows large discharge amount, small water quality change, stable and generally higher salt content, and especially higher chloride ion content, and the composition form mainly stores organic matters and inorganic matters, wherein the ammonia nitrogen content is lower, the Chemical Oxygen Demand (COD) is generally 600mg/L, the Total Dissolved Solids (TDS) is 10000 + 80000mg/L, the calcium and magnesium content is high, and the high-salt water contains sulfate radicals and other easily-scaling ions. The direct discharge of the high-salinity wastewater not only can cause soil hardening, salinization, crop damage and ecological environment deterioration in a discharge area, but also indirectly wastes the related early investment of water taking, pretreatment and the like in the desalted water production process, thereby increasing the water production cost. Therefore, the realization of the recycling of the saline wastewater in the coal chemical industry is one of the problems to be solved urgently at present.
Zero emission is an effective way for recycling the salt-containing wastewater. Membrane concentration and evaporative crystallization are important links of the 'zero emission' process. The existence of organic matters can cause the pollution blockage of the membrane and the increase of cleaning, and influence the flux of the membrane and the recovery rate of water. In addition, organic substances also affect the crystal formation of the salt and the quality of the crystallized salt. Therefore, effective removal of organics from the high-salt water must be considered.
The method for removing organic matters in the high-salt water comprises coagulation, adsorption and advanced oxidation. Coagulation/flocculation is a traditional removal method, and has a good removal effect on macromolecular organic matters, and the removal rate is usually about 30%. The advanced oxidation technology can mineralize or decompose part of organic matters in the wastewater, and can effectively remove the organic matters in the reverse osmosis concentrated solution. The Fenton technology and the ozone catalytic oxidation technology have obvious effects, the removal rate can reach 60%, but the medicament consumption is high, and the cost is high. Activated carbon adsorption is a common process in a water treatment process, particularly, powdered carbon has good removal effect on organic matters, and the removal rate of the organic matters can reach 70%. However, activated carbon mainly adsorbs small molecular organic substances, and the cost is high due to the separation and regeneration of powdery carbon.
A method (CN201510055332.4) for degrading COD in nanofiltration concentrated brine discloses a method for degrading COD in the nanofiltration concentrated brine, wherein the COD can be reduced to within 100 from 273 by carrying out zero-valent iron reaction, electrolysis reaction, indirect Fenton reaction, catalytic oxidation reaction, coagulating sedimentation and photocatalytic reaction on the nanofiltration concentrated brine to degrade and decompose organic matters in the nanofiltration concentrated brine. The technical scheme has complex process.
A biological treatment method (CN105645599A) of reverse osmosis strong brine discloses a biological treatment method of reverse osmosis strong brine, wherein the salt content of the reverse osmosis strong brine is 1-6%, the COD Cr concentration is 100-1000mg/L, the ammonia nitrogen concentration is 1-10mg/L, the B/C ratio (biochemical oxygen demand/chemical oxygen demand) is lower than 0.2, immobilized high salt-resistant COD degrading bacteria are added, meanwhile, continuous aeration is carried out for treatment for 5-20h, then, composite synergistic components are added, and water is collected after aeration treatment is continued for 20-60 h; or adding the composite synergistic component while adding the immobilized high-salt-resistance COD degrading bacteria, carrying out continuous aeration, and collecting the effluent after 5-80h of treatment. The biological method has long treatment time and occupies much land.
Disclosure of Invention
Aiming at the problems of limited technical efficiency and high treatment cost of removing organic matters in the high-salinity wastewater zero-discharge process, the invention provides the method for reducing COD in the high-salinity wastewater zero-discharge process in the coal chemical industry, by adopting the technical scheme, the organic matters in the high-salinity wastewater can be effectively reduced, the removal rate of COD can reach about 80%, and the cost is reduced by 1/4.
The invention provides a method for treating wastewater, which comprises the following steps: oxidizing the homogenized wastewater in an oxidation pond; introducing the wastewater after oxidation treatment into a coagulation tank for coagulation; introducing the wastewater subjected to coagulation treatment into an adsorption tank, and adding an adsorbent for adsorption; and carrying out solid-liquid separation on the wastewater after the adsorption treatment.
In the above method, wherein the homogenized wastewater is oxidized by adding potassium permanganate.
In the method, the concentration of the potassium permanganate is 40-80mg/L, and the oxidation reaction time is 30-60 min.
In the above method, the coagulant used for the coagulation treatment is an iron-based coagulant.
In the above method, the iron-based coagulant is polyferric sulfate.
In the method, the adding amount of the coagulant is 200-600mg/L, and the coagulation reaction time is 3-5 min.
In the above method, wherein the adsorbent is activated coke.
In the method, the adding amount of the adsorbent is 0.5-1.5g/L, and the adsorption time is 60-90 min.
In the above method, wherein, in the solid-liquid separation, the retention time of the wastewater is 1 to 2 hours.
In the above method, wherein the solid-liquid separation is effected by inclined plate precipitation, microfiltration membrane filtration or cyclone separation.
The potassium permanganate changes the structures of substances such as the scale inhibitor, the dispersing agent and the like, so that colloids and particles in the water body are destabilized, and organic matters are easy to polymerize, thereby improving the removal of the organic matters. The reaction product, namely the nascent hydrated manganese dioxide, can not only catalyze and oxidize organic matters, but also adsorb the organic matters to form compact flocs, so that the size of the flocs is obviously increased, and solid-liquid separation is facilitated.
The coagulant is added, the mixture is quickly stirred, and then the activated coke is added, so that a better coagulation strengthening effect can be obtained. The colloid in the water forms particles with certain granularity after destabilization, is difficult to participate in competitive adsorption on the surface of the active coke, and simultaneously, the active coke is more favorable for removing the organic components with solubility in the water due to the two effects because macromolecular organic matters are removed during rapid stirring. On the other hand, the active coke is added after the rapid stirring, so that the influence of floc wrapping on the active coke can be reduced, the added active coke is mostly attached to the surface of the floc, the function of adsorbing organic matters is better exerted, and the solid-liquid separation is strengthened.
Through the integration of several technologies, the effective removal of organic matters is realized, and the removal rate of COD can reach 70-80%. By technical integration, synergy is achieved, and processing cost is reduced 1/4.
Drawings
Figure 1 shows an apparatus for treating high salinity wastewater. In fig. 1, 1 is an oxidation tank, 2 is a coagulation tank, 3 is an adsorption tank, and 4 is a solid-liquid separation unit.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The technical scheme provided by the invention integrates three main processes of oxidation, coagulation and adsorption to remove organic matters in the high-salinity water, and plays a synergistic effect of the three processes. Aiming at the condition that high-salt water contains a dispersing agent, a scale inhibitor and natural organic matters, the structure of partial organic matters is changed by adopting oxidation treatment, and the removal effect of coagulation on the substances is enhanced. Removing the micromolecular organic matters by active coke adsorption.
The method comprises the following steps:
and (3) oxidation: the homogenized high-salinity wastewater enters an oxidation pond, an oxidant potassium permanganate is added, the concentration of the potassium permanganate is 40-80mg/L, and the reaction time is 30-60 min;
coagulation: the wastewater after oxidation treatment enters a coagulation tank, the coagulant is an iron-based coagulant, the adding amount of the coagulant is 200-600mg/L, and the coagulation reaction time is 3-5 min;
adsorption: the waste water after the coagulation stirring enters an adsorption tank, and powdered active coke is added, wherein the adding amount is 0.5-1.5g/L, and the adsorption time is 60-90 min.
Solid-liquid separation: solid-liquid separation is realized through inclined plate precipitation, microfiltration membrane filtration or cyclone separation, and the retention time is 1-2 h.
The following description will be given with reference to specific examples.
Example 1 desalination of salt-containing Water of a coal chemical industry park first-order concentrated Water, COD 350mg/L, TDS 10000mg/L
The high-salinity wastewater containing organic matters firstly enters an oxidation pond, the adding amount of potassium permanganate is 40mg/L, and the reaction time is 30 min; then the mixture enters a coagulation tank, the dosage of the polymeric ferric sulfate is 400mg/L, the mixture is stirred and reacts for 3min, the effluent enters an adsorption tank, the dosage of the active coke is 0.5g/L, and the adsorption time is 60 min; the water after adsorption treatment enters a solid-liquid separation unit, the retention time is 60min, and the separated water enters a subsequent treatment unit. After the treatment of the steps, the COD of the high-salt water is reduced from 350mg/L to 60mg/L, and the treatment cost of each ton of water is about 2.5 yuan.
Example 2 desalination of salt-containing Water of a coal chemical industry park Secondary concentrated Water, COD 500mg/L, TDS 18000mg/L
The high-salinity wastewater containing organic matters firstly enters an oxidation pond, the adding amount of potassium permanganate is 80mg/L, and the reaction time is 60 min; then the mixture enters a coagulation tank, the adding amount of the polymeric ferric sulfate is 600mg/L, the mixture is stirred and reacts for 5min, the effluent enters an adsorption tank, the adding amount of the active coke is 1.5g/L, and the adsorption time is 90 min; the water after adsorption treatment enters a solid-liquid separation unit, the retention time is 90min, and the separated water enters a subsequent treatment unit. After the treatment of the steps, the COD of the high-salt water is reduced from 500mg/L to 96mg/L, and the treatment cost of each ton of water is about 3.5 yuan.
Example 3 desalination of salt-containing Water of a coal chemical industry park first-order concentrated Water, COD 450mg/L, TDS 15000mg/L
The high-salinity wastewater containing organic matters firstly enters an oxidation pond, the adding amount of potassium permanganate is 60mg/L, and the reaction time is 45 min; then the mixture enters a coagulation tank, the dosage of the polymeric ferric sulfate is 200mg/L, the mixture is stirred and reacts for 4min, the effluent enters an adsorption tank, the dosage of the active coke is 1.0g/L, and the adsorption time is 75 min; the water after adsorption treatment enters a solid-liquid separation unit, the retention time is 120min, and the separated water enters a subsequent treatment unit. After the treatment of the steps, the COD of the high-salt water is reduced from 450mg/L to 71mg/L, and the treatment cost of each ton of water is about 3.0 yuan.
The potassium permanganate changes the structures of substances such as the scale inhibitor, the dispersing agent and the like, so that colloids and particles in the water body are destabilized, and organic matters are easy to polymerize, thereby improving the removal of the organic matters. The reaction product, namely the nascent hydrated manganese dioxide, can not only catalyze and oxidize organic matters, but also adsorb the organic matters to form compact flocs, so that the size of the flocs is obviously increased, and solid-liquid separation is facilitated.
The coagulant is added, the mixture is quickly stirred, and then the activated coke is added, so that a better coagulation strengthening effect can be obtained. The colloid in the water forms particles with certain granularity after destabilization, is difficult to participate in competitive adsorption on the surface of the active coke, and simultaneously, the active coke is more favorable for removing the organic components with solubility in the water due to the two effects because macromolecular organic matters are removed during rapid stirring. On the other hand, the active coke is added after the rapid stirring, so that the influence of floc wrapping on the active coke can be reduced, the added active coke is mostly attached to the surface of the floc, the function of adsorbing organic matters is better exerted, and the solid-liquid separation is strengthened.
Through the integration of several technologies, the effective removal of organic matters is realized, and the removal rate of COD can reach 70-80%. By technical integration, synergy is achieved, and processing cost is reduced 1/4.
Those skilled in the art will appreciate that the above embodiments are merely exemplary embodiments and that various changes, substitutions, and alterations can be made without departing from the spirit and scope of the invention.
Claims (8)
1. A method for treating high-salinity wastewater containing organic matters, comprising the following steps:
oxidizing the homogenized wastewater in an oxidation pond;
introducing the wastewater after oxidation treatment into a coagulation tank for coagulation;
stirring the wastewater after coagulation treatment, introducing the wastewater into an adsorption tank, and adding an active coke adsorbent for adsorption; and
the solid-liquid separation is carried out on the wastewater after the adsorption treatment,
wherein the adding amount of the active coke adsorbent is 0.5-1.5g/L, the adsorption time is 60-90min,
wherein before entering the oxidation pond, the chemical oxygen demand of the high-salt wastewater containing the organic matters is between 350 and 500 mg/L.
2. The method for treating high-salinity wastewater containing organic substances according to claim 1, wherein the homogenized wastewater is oxidized by adding potassium permanganate.
3. The method for treating wastewater containing organic substances and high salt according to claim 2, wherein the concentration of potassium permanganate is 40-80mg/L, and the oxidation reaction time is 30-60 min.
4. The method for treating high-salinity wastewater containing organic substances according to claim 1, wherein the coagulant used for the coagulation treatment is an iron-based coagulant.
5. The method for treating wastewater containing high salt of organic matter according to claim 4, wherein the iron-based coagulant is polyferric sulfate.
6. The method for treating high-salinity wastewater containing organic matters according to claim 4, wherein the addition amount of the coagulant is 200-600mg/L, and the coagulation reaction time is 3-5 min.
7. The method for treating high-salinity wastewater containing organic matter according to claim 1, wherein the residence time of the wastewater in the solid-liquid separation is 1-2 h.
8. The method for treating high-salinity wastewater containing organic matter according to claim 1, wherein the solid-liquid separation is achieved by inclined plate precipitation, microfiltration membrane filtration or cyclone separation.
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| CN1513777A (en) * | 2003-03-17 | 2004-07-21 | 哈尔滨工业大学 | Permangnate preoxidation and bioactive carbon combined use to remove contamination technique |
| CN104556469A (en) * | 2013-10-25 | 2015-04-29 | 北大方正集团有限公司 | Organic waste liquid treatment method |
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| CN104556469A (en) * | 2013-10-25 | 2015-04-29 | 北大方正集团有限公司 | Organic waste liquid treatment method |
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