CN110563221A - Treatment system and method for high-saline-alkali slag wastewater - Google Patents
Treatment system and method for high-saline-alkali slag wastewater Download PDFInfo
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- CN110563221A CN110563221A CN201910922792.0A CN201910922792A CN110563221A CN 110563221 A CN110563221 A CN 110563221A CN 201910922792 A CN201910922792 A CN 201910922792A CN 110563221 A CN110563221 A CN 110563221A
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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
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/465—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electroflotation
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur 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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Abstract
The invention discloses a treatment system for high-saline-alkali residue wastewater, which comprises a pH adjusting unit, an electric floatation unit, an electric flocculation unit and an electric catalytic oxidation unit which are sequentially arranged, wherein the electric floatation unit comprises an electric floatation device; the electric flocculation unit comprises electric flocculation equipment and solid-liquid separation equipment; the electrocatalytic oxidation unit comprises an electrocatalytic oxidation device. In addition, the invention also discloses a method for treating the high-saline-alkali residue wastewater, which comprises the following steps: 1) adjusting the pH value of the high-saline-alkali residue wastewater to 5-8, and standing for layering; 2) carrying out electric floating treatment on the lower-layer wastewater in the step 1); 3) performing electric flocculation treatment on the electric air-floated effluent, and performing solid-liquid separation on the effluent generated by the electric flocculation treatment; 4) carrying out electrocatalytic oxidation treatment on the liquid-phase effluent in the step 3). The treatment system and the method can realize the high-efficiency, economic and environment-friendly treatment of the high-saline-alkali residue wastewater at normal temperature and normal pressure.
Description
Technical Field
The invention relates to a system and a method for treating high-salinity and alkalinity slag wastewater, in particular to an electrochemical treatment technology for phenols and sulfides in the high-salinity and alkalinity slag wastewater, and belongs to the technical field of sewage treatment in petrochemical industry.
Background
In the process of oil refining or ethylene production, in order to prevent indexes such as sulfur content, corrosivity and acidity in finished oil from exceeding standards, alkali washing refining is usually adopted, that is, sodium hydroxide solution and acidic substances in the oil product are adopted to react to generate salts which are insoluble in the oil product, and then the salts are discharged in the form of alkali residues.
the caustic sludge wastewater belongs to organic wastewater with high concentration, high toxicity, difficult degradation, deep color, odor and strong corrosiveness, and contains high-concentration thioether, mercaptan, sulfide, oil, impure phenol, organic acid salt and other inorganic compounds. Although the high saline-alkali residue wastewater occupies a small amount, generally only 5-10%, the discharge amount of the high saline-alkali residue wastewater is up to 30-60% of the total discharge amount of pollutants, and the high saline-alkali residue wastewater is a main source of the odor of an oil refinery. If the oil refining high saline-alkali residue wastewater is not properly treated, the wastewater can cause serious pollution to the atmosphere, water environment and the like of an oil refining enterprise, and the normal operation of a sewage treatment plant is influenced.
aiming at the characteristics of high phenol, high sulfur, high salt and difficult biochemical degradation of the alkaline residue wastewater, scholars at home and abroad carry out a series of research and study. The method of combining Fenton and biological treatment or wet oxidation and biological treatment, which is most commonly used at present, has a high COD removal rate, but requires the addition of a large amount of chemical agents and causes secondary pollution. In addition, the method needs to dilute the high-salinity waste water, and a large amount of dilution water is needed, and the occupied area of equipment is large. Although the wet oxidation process can be used for relatively thorough treatment, the technology needs to be operated at high temperature and high pressure, the investment and operation cost is high, and the equipment is seriously corroded.
CN101758057A discloses an oil refining alkaline residue high-efficiency harmless treatment method, which adopts the first two-stage biological primary and middle-stage ozone catalytic oxidation technology, the technology needs a large amount of water to dilute the high-saline-alkaline residue wastewater by 20 times, and meanwhile, the content of butter in the ethylene alkaline residue has great influence on the stable operation of the device and is easy to block biological filter screens and catalyst fillers. CN1050012A discloses a combined process of wet oxidation and anaerobic bio-digestion/aerobic bio-treatment, which can oxidize most of organic matters, and the excess sludge from aerobic bio-treatment enters a wet oxidation unit, and the whole process does not discharge the excess sludge. CN102877351A discloses a method for treating high-concentration alkali liquor, which comprises the steps of carrying out wet air oxidation on waste liquor at 100-190 ℃, then adding acid for acidification to recover phenol and naphthenic acid, and finally introducing the waste water into an SBR reactor for treatment.
At present, the high saline-alkali slag wastewater treatment technology with engineering cases at home and abroad mainly adopts a wet oxidation method, such as a mild wet oxidation technology of the research institute, a Zimpro technology of the United states, a JAC technology of Japan, and a SK bio-enhancement technology of Korea, and the treatment scale is generally 1.0-2.5 m3The investment per ton of water is 370-2800 thousands and the operation cost is 80-150 yuan/m3(without equipment depreciation and labor cost). Therefore, the investment and the operation cost of the prior process technology are high, and the high-temperature high-pressure high-salt sewage has strong corrosivity and seriously influences the service life of equipment. Therefore, how to reduce the investment and the operating cost of the high saline-alkali residue wastewater and improve the biodegradability of the sewage is a problem to be solved urgently in the field on the premise of ensuring the treatment effect of the high saline-alkali residue wastewater.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a treatment system for treating high-salinity and alkalinity waste water by combining physical chemistry and electrochemistry at normal temperature and normal pressure, can solve the problems of high investment and high operating cost of the high-salinity and alkalinity waste water in the prior art, and realizes the high-efficiency, economic and environment-friendly treatment effect on the high-salinity and alkalinity waste water. In addition, the invention also aims to provide a treatment method for treating the high-saline-alkali slag wastewater by using the treatment system.
in order to achieve the purpose, the invention adopts the following technical scheme:
The treatment system for the high-saline-alkali slag wastewater comprises a pH adjusting unit, an electric floating unit, an electric flocculation unit and an electric catalytic oxidation unit which are sequentially arranged, wherein the pH adjusting unit is used for adjusting the pH value of the high-saline-alkali slag wastewater to 5-8, and the electric floating unit comprises an electric air floating device; the electric flocculation unit comprises electric flocculation equipment and solid-liquid separation equipment, and the effluent of the electric air floatation device sequentially enters the electric flocculation equipment and the solid-liquid separation equipment; the electrocatalytic oxidation unit comprises electrocatalytic oxidation equipment and filtering equipment, and effluent of the solid-liquid separation equipment sequentially enters the electrocatalytic oxidation equipment.
Further: the pH adjusting unit comprises a pH adjusting tank, and sulfuric acid or hydrochloric acid is added into the pH adjusting tank; and when the acid added into the pH adjusting tank is sulfuric acid, the anode of the electro-flotation device adopts a titanium-coated lead dioxide electrode, when the acid added into the pH adjusting tank is hydrochloric acid, the anode of the electro-flotation device adopts a titanium-coated lead dioxide electrode or a titanium-coated ruthenium iridium electrode, and the cathode of the electro-flotation device is any one of titanium, graphite, 304 stainless steel, 304L stainless steel, 316 stainless steel or 316L stainless steel.
Further: the electric flocculation equipment is high-frequency pulse electric flocculation equipment, the electrode material of the high-frequency pulse electric flocculation equipment is iron, aluminum, iron-aluminum-zinc alloy or graphite, and a single-pulse or double-pulse direct-current power supply with the frequency of more than 1000Hz is adopted as a power supply.
Further: the electrode of the electrocatalytic oxidation equipment is a titanium-based lead dioxide electrode with a nanocrystalline film coating, the cathode of the electrocatalytic oxidation equipment is a stainless steel or titanium plate, and the main structure of the electrocatalytic oxidation equipment is made of PP, PE or UPVC.
Further: the pH value of the effluent of the electric flocculation equipment is adjusted back to 8-10, and then the effluent enters solid-liquid separation equipment for solid-liquid separation; and adjusting the pH value of the effluent of the solid-liquid separation equipment to 4-6, then feeding the effluent into the electrocatalytic oxidation equipment, adjusting the pH value of the effluent of the electrocatalytic oxidation equipment to 6-9, and then feeding the effluent into a water producing tank.
Another object of the present invention is a method for treating high saline-alkali slag wastewater by using the treatment system, which comprises the following treatment steps:
1) Adjusting the pH value of the high-saline-alkali residue wastewater to 5-8, standing until the wastewater is layered, recovering crude phenol, naphthenic acid and oil on the upper layer, and treating the wastewater on the lower layer in the next treatment step;
2) carrying out electric floatation treatment on the lower-layer wastewater subjected to the acid adjustment treatment in the step 1) to generate scum and electric floatation effluent;
3) The method comprises the following steps of carrying out electric flocculation treatment on the electric floating effluent by using an electric flocculation device, and carrying out solid-liquid separation on the effluent generated by the electric flocculation treatment to generate solid-phase sludge and liquid-phase effluent, wherein the electric flocculation device is high-frequency pulse electric flocculation equipment, electrodes of the high-frequency pulse electric flocculation equipment are made of iron, aluminum, iron-aluminum-zinc alloy or graphite, and a power supply of the high-frequency pulse electric flocculation equipment adopts a frequency single-pulse or double-pulse direct-current power supply with the frequency greater than 1000 Hz;
4) And (3) feeding the liquid phase effluent in the step 3) into an electrocatalytic oxidation device for electrocatalytic oxidation treatment, wherein an electrode of the electrocatalytic oxidation device is a titanium-based lead dioxide electrode with a nanocrystalline film coating, a cathode of the electrocatalytic oxidation device is stainless steel or a titanium plate, and the main structure of the electrocatalytic oxidation device is made of PP, PE or UPVC.
Further: in the electric flocculation treatment in the step 3), the voltage is 0-220V, and the current density is 0-30 mA/cm2The treatment time is 20-40 min.
Further: in the step 3), the pH value of effluent generated by the electrocoagulation treatment is adjusted to 8-10, and then solid-liquid separation treatment is carried out.
Further: in the step 4), the pH value of liquid phase effluent obtained by solid-liquid separation is adjusted to 4-6, and then electrocatalytic oxidation treatment is carried out.
further: in the electrocatalytic oxidation treatment in the step 4), the voltage is 0-12V, and the current density is 5-40 mA/cm2The treatment time is 30-120 min.
The system and the method have the beneficial effects that the system and the method treat the high-salinity and alkaline residue wastewater by using the physical chemistry and electrochemical process at normal temperature and normal pressure so as to remove sulfides and organic matters in the high-salinity and alkaline residue wastewater, reduce COD (chemical oxygen demand) and toxicity of the wastewater, improve the biodegradability of the wastewater, and effectively recover crude phenol and naphthenic acid. In addition, the processing system has the advantages of small equipment occupation area, lower investment and operation cost, high automation degree and better application prospect.
Drawings
FIG. 1 shows a block diagram of a process for treating high saline-alkali residue wastewater according to the invention.
Detailed Description
The following further describes the embodiments of the present invention with reference to the drawings.
According to one aspect of the invention, the treatment system of the high saline-alkali residue wastewater comprises a pH adjusting unit, an electric floating unit, an electric flocculation unit and an electric catalytic oxidation unit which are sequentially arranged, wherein the pH adjusting unit comprises a pH adjusting tank, the high saline-alkali residue wastewater from an oil refinery or an ethylene plant enters the pH adjusting tank, acid can be added into the pH adjusting tank to adjust the pH value of the high saline-alkali residue wastewater to 5-8, crude phenol, naphthenic acid and petroleum in the upper layer can be recovered after standing and layering, and the wastewater in the lower layer enters the electric floating unit. The electric floating unit comprises an electric floating device for carrying out electric floating treatment on the wastewater which is sent by the pH adjusting unit and is subjected to acid adjusting treatment so as to realize preoxidation gel breaking, emulsion breaking and air floating separation of the wastewater, scum generated by the treatment of the electric floating device can be sent to the existing scum treatment system in a field for further treatment, and the effluent of the scum enters the electric flocculation unit. The electric flocculation unit comprises electric flocculation equipment and solid-liquid separation equipment, wherein the electric flocculation equipment is preferably high-frequency pulse electric flocculation equipment, 32 wt% of sodium hydroxide solution is used for returning the wastewater treated by the high-frequency pulse electric flocculation equipment to pH 8-10, then the wastewater enters the solid-liquid separation equipment for solid-liquid separation, the sludge generated by separation can be sent to an existing sludge treatment unit in a field for further treatment, and the effluent generated by separation is sent to an electric catalytic oxidation unit. In the invention, the electrocatalytic oxidation unit can comprise electrocatalytic oxidation equipment, and the pH of effluent water generated by the separation of solid-liquid separation equipment of the electrocaloric unit is adjusted to 4-6, and then the effluent water enters the electrocatalytic oxidation equipment to be subjected to electrocatalytic oxidation treatment to deeply remove phenols, sulfides and organic matters in wastewater. And adjusting the pH value of the effluent of the electrocatalytic oxidation equipment to 6-9, and then sending the effluent into a water producing tank, wherein COD (chemical oxygen demand) of the effluent in the water producing tank is less than 800mg/l, sulfides is less than 20mg/l, phenols are less than 20mg/l, and the water inlet requirement of a subsequent sewage treatment plant can be met. In addition, the treatment system also comprises a connecting pipeline and a lift pump which are arranged among the treatment units. Moreover, the processing system can also comprise a PLC control unit for automatically controlling each unit.
According to another aspect of the invention, a method for treating high saline-alkali residue wastewater is also provided, which comprises the following treatment steps:
1) And (3) pH adjustment: the method comprises the following steps of lifting high-saline-alkali residue wastewater of an oil refining or ethylene plant into a pH adjusting tank through a pump, adding an acid such as 98% sulfuric acid or 31% hydrochloric acid into the pH adjusting tank to adjust the pH value of the wastewater to 5-8, allowing the wastewater to stay and stand in the pH adjusting tank for 2-10 hours, recovering upper-layer crude phenol, naphthenic acid and petroleum generated by layering, and allowing the lower-layer wastewater to enter an electric floating unit for electric floating treatment;
2) Electro-flotation treatment: lifting the lower-layer wastewater in the pH adjusting tank by a pump, and allowing the wastewater to enter an electric floatation device for electric floatation treatment for 10-60 min to realize preoxidation gel breaking, emulsion breaking and air floatation separation of the wastewater, wherein in the step, when the acid adjusting reagent added in the pH adjusting process in the step 1) is sulfuric acid, the anode of the electric floatation device in the step can adopt a titanium-coated lead dioxide electrode, and when the acid adjusting reagent added in the step 1) is hydrochloric acid, the anode of the electric floatation device can adopt a titanium-coated lead dioxide electrode or a titanium-coated ruthenium iridium electrode, and meanwhile, the cathode of the electric floatation device can adopt any one of 304 stainless steel, 304L stainless steel, 316 stainless steel or 316L stainless steel. Scum generated by the electric floating treatment can be sent to a scum treatment unit for further treatment, and the effluent of the scum can enter an electric flocculation unit for electric flocculation treatment;
3) Electric flocculation treatment: the effluent water generated by the electro-flotation treatment is pumped into an electro-flocculation device at a voltage of 0-220V and a voltage of 0-30 mA/cm2Performing electric flocculation treatment for 20-40 min under the current density. The electric flocculation device is preferably high-frequency pulse electric flocculation equipment, the electrode of the high-frequency pulse electric flocculation equipment is made of iron, aluminum, iron-aluminum-zinc alloy or graphite, and a power supply of the high-frequency pulse electric flocculation equipment adopts a high-frequency single pulse with the frequency of more than 1000HzOr a high-frequency double-pulse direct-current power supply, and the main structure of the electric flocculation equipment adopts a carbon steel anticorrosive material. Adjusting the pH value of the wastewater after the electrocoagulation treatment to 8-10 at the water outlet of the electrode by using 32 wt% sodium hydroxide solution, then feeding the wastewater into a solid-liquid separation device for solid-liquid separation, wherein solid-phase sludge generated by separation can be sent to the existing sludge treatment system in a field for further treatment, and liquid-phase effluent generated by separation can enter an electrocatalytic oxidation unit;
4) electrocatalytic oxidation treatment: adjusting the pH value of effluent generated in the step 3) after solid-liquid separation to 4-6, feeding the effluent into an electrocatalytic oxidation device, and controlling the voltage at 0-12V and the voltage at 5-40 mA/cm2Carrying out electrocatalytic oxidation treatment for 30-120 min under the current density of the wastewater, and deeply removing phenols, sulfides and organic matters in the wastewater; wherein, the electrode of the electrocatalytic oxidation equipment is a titanium-based lead dioxide electrode with a nano-crystal film coating, the cathode of the electrocatalytic oxidation equipment is a stainless steel or titanium plate, and the main structure of the equipment is made of PP, PE or UPVC; and (3) returning the effluent after the electrocatalytic oxidation treatment to the pH value of 6-9, and then sending the effluent into a water producing tank, wherein the COD (chemical oxygen demand) of the sewage in the water producing tank is less than 800mg/l, the sulfide is less than 20mg/l, and the phenols are less than 20mg/l, so that the water inlet requirement of a subsequent sewage treatment plant can be met.
in the high-saline-alkali residue wastewater of oil refining or ethylene plants, the sulfide, the phenol, the salt content and the like are high, and the biodegradability is poor. The treatment system and the method are adopted to treat the sewage at normal temperature and normal pressure through an electrochemical technology, and each treatment unit adopts the current density of 5-30 mA/cm in the treatment process2The direct current can not produce secondary pollution to, the preferred airtight processing of each processing unit, tail gas are unified to be collected and are carried to the present tail gas processing system in the scene and handle, only need to adjust voltage, current density and pH according to the quality of water coming and can accomplish whole waste water treatment process, have simple process reliable, investment cost is little, advantage that the running cost is low.
example 1
Processing 1.0m with the processing system and method of the present invention as described above3the waste water of catalytic gasoline high saline-alkali residue in a certain refinery contains COD49800mg/L, sulfide 8540mg/L and volatile phenol 8600 mg/L. The whole treatment process comprises the following steps:
1) The high saline-alkali residue wastewater enters a pH adjusting tank, sulfuric acid is added into the adjusting tank to adjust the pH value of the wastewater to 7, the wastewater is kept stand for 8 hours until the wastewater is demulsified and layered, crude phenol, naphthenic acid and oil on the upper layer are recovered, and the wastewater on the lower layer enters electric floating equipment;
2) in the electric floating device, waste water is subjected to preoxidation gel breaking and emulsion breaking under the action of electricity, organic sulfur and the like in the waste water are converted into inorganic sulfur, and meanwhile, phenol molecules are degraded and decolored. Scum generated by the electric floating treatment can be sent to a scum treatment unit for further treatment, and the effluent of the scum is lifted by a pump and enters high-frequency pulse electric flocculation equipment;
3) The effluent water of the electro-flotation treatment is at the voltage of 120V and 20mA/cm in an electro-flocculation device2The electric flocculation treatment is carried out for 30min under the current density, polymeric flocculants such as PAC (polyaluminium chloride), PFS (PFS) and the like do not need to be introduced in the treatment process, and meanwhile, the flocculation efficiency is high and the sludge yield is low due to double functions of an electric field and electrodes. The pH value of the wastewater after the electric flocculation treatment is adjusted back to 9 at the water outlet of the electrode by using a 32 wt% d sodium hydroxide solution to form an optimal environment for flocculation and precipitation, sulfides and original sulfides generated by pre-oxidation are removed, solid-liquid separation is carried out by solid-liquid separation equipment, solid-phase sludge generated by separation can be sent to a sludge treatment unit for further treatment, and cleaner sewage generated by separation can enter electrocatalytic oxidation equipment;
4) The effluent of the electric flocculation equipment is adjusted to pH 5 in a pipeline and then enters into an electric catalytic oxidation equipment at the voltage of 10V and the voltage of 25mA/cm2The treatment is carried out for 60min under the current, the phenol, the sulfur and the organic matters are deeply removed, and the effluent quality is controlled by adjusting the operating parameters of the electrocatalytic oxidation.
after the gasoline high-saline-alkali residue wastewater is treated, the effluent water has the COD of 700mg/L, the BOD of 240mg/L, the B/C of 0.34, the sulfide of 10mg/L and the volatile phenol of 15mg/L, is clear, has good biodegradability and has no significant odor.
Example 2
the treatment system and the method for treating the high saline alkali of the ethylene1.0m of slag waste water3the COD in the wastewater is 25000mg/L, the sulfide is 10000mg/L, and the volatile phenol is 8000 mg/L. The whole process is similar to that of embodiment 1, and is not described herein again. After the ethylene high-saline-alkali slag wastewater is treated, the effluent water has COD550mg/L, BOD200mg/L, B/C0.36, 12mg/L of sulfide and 18mg/L of volatile phenol, and is clear, good in biodegradability and free of significant odor.
The present invention has been described in detail with reference to the preferred embodiments. However, variations and additions to the embodiments will become apparent to those of ordinary skill in the art upon a reading of the foregoing description. It is the intention of the applicants that all such variations and additions fall within the scope of the claims. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Any modification and improvement of this product, and the substitution and use of the same or similar substances within the scope or range of patents, shall fall within the scope of protection of this invention.
Claims (10)
1. The utility model provides a processing system of high saline and alkaline sediment waste water which characterized in that: the device comprises a pH adjusting unit, an electric floating unit, an electric flocculation unit and an electric catalytic oxidation unit which are sequentially arranged, wherein the pH adjusting unit is used for adjusting the pH value of the high-saline-alkali slag wastewater to 5-8, and the electric floating unit comprises an electric air floating device; the electric flocculation unit comprises electric flocculation equipment and solid-liquid separation equipment, and the effluent of the electric air floatation device sequentially enters the electric flocculation equipment and the solid-liquid separation equipment; the electrocatalytic oxidation unit comprises electrocatalytic oxidation equipment and filtering equipment, and effluent of the solid-liquid separation equipment sequentially enters the electrocatalytic oxidation equipment.
2. The processing system of claim 1, wherein: the pH adjusting unit comprises a pH adjusting tank, and sulfuric acid or hydrochloric acid is added into the pH adjusting tank; and when the acid added into the pH adjusting tank is sulfuric acid, the anode of the electro-flotation device adopts a titanium-coated lead dioxide electrode, when the acid added into the pH adjusting tank is hydrochloric acid, the anode of the electro-flotation device adopts a titanium-coated lead dioxide electrode or a titanium-coated ruthenium iridium electrode, and the cathode of the electro-flotation device is any one of titanium, graphite, 304 stainless steel, 304L stainless steel, 316 stainless steel or 316L stainless steel.
3. The processing system of claim 1, wherein: the electric flocculation equipment is high-frequency pulse electric flocculation equipment, the electrode material of the high-frequency pulse electric flocculation equipment is iron, aluminum, iron-aluminum-zinc alloy or graphite, and a single-pulse or double-pulse direct-current power supply with the frequency of more than 1000Hz is adopted as a power supply.
4. the processing system of claim 1, wherein: the electrode of the electrocatalytic oxidation equipment is a titanium-based lead dioxide electrode with a nanocrystalline film coating, the cathode of the electrocatalytic oxidation equipment is a stainless steel or titanium plate, and the main structure of the electrocatalytic oxidation equipment is made of PP, PE or UPVC.
5. The processing system of claim 1, wherein: the pH value of the effluent of the electric flocculation equipment is adjusted back to 8-10, and then the effluent enters solid-liquid separation equipment for solid-liquid separation; and adjusting the pH value of the effluent of the solid-liquid separation equipment to 4-6, then feeding the effluent into the electrocatalytic oxidation equipment, adjusting the pH value of the effluent of the electrocatalytic oxidation equipment to 6-9, and then feeding the effluent into a water producing tank.
6. A method for treating high saline-alkali slag wastewater by using the treatment system as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps: the method comprises the following processing steps:
1) Adjusting the pH value of the high-saline-alkali residue wastewater to 5-8, standing until the wastewater is layered, recovering crude phenol, naphthenic acid and oil on the upper layer, and treating the wastewater on the lower layer in the next treatment step;
2) Carrying out electric floating treatment on the lower-layer wastewater subjected to the acid adjustment treatment in the step 1);
3) The method comprises the following steps of carrying out electric flocculation treatment on the electric floating effluent by using an electric flocculation device, and carrying out solid-liquid separation on the effluent generated by the electric flocculation treatment to generate solid-phase sludge and liquid-phase effluent, wherein the electric flocculation device is high-frequency pulse electric flocculation equipment, electrodes of the high-frequency pulse electric flocculation equipment are made of iron, aluminum, iron-aluminum-zinc alloy or graphite, and a power supply of the high-frequency pulse electric flocculation equipment adopts a single-pulse or double-pulse direct current power supply with the frequency of more than 1000 Hz;
4) And (3) feeding the liquid phase effluent in the step 3) into an electrocatalytic oxidation device for electrocatalytic oxidation treatment, wherein an electrode of the electrocatalytic oxidation device is a titanium-based lead dioxide electrode with a nanocrystalline film coating, a cathode of the electrocatalytic oxidation device is stainless steel or a titanium plate, and the main structure of the electrocatalytic oxidation device is made of PP, PE or UPVC.
7. the processing method according to claim 6, characterized in that: in the electric flocculation treatment in the step 3), the voltage is 0-220V, and the current density is 0-30 mA/cm2The treatment time is 20-40 min.
8. The processing method according to claim 6 or 7, characterized in that: in the step 3), the pH value of effluent generated by the electrocoagulation treatment is adjusted to 8-10, and then solid-liquid separation treatment is carried out.
9. The processing method according to claim 6 or 7, characterized in that: in the step 4), the pH value of liquid phase effluent obtained by solid-liquid separation is adjusted to 4-6, and then electrocatalytic oxidation treatment is carried out.
10. The processing method according to claim 6 or 7, characterized in that: in the electrocatalytic oxidation treatment in the step 4), the voltage is 0-12V, and the current density is 5-40 mA/cm2The treatment time is 30-120 min.
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