WO2020258359A1 - 强化上流式多相废水氧化处理工艺及处理系统 - Google Patents

强化上流式多相废水氧化处理工艺及处理系统 Download PDF

Info

Publication number
WO2020258359A1
WO2020258359A1 PCT/CN2019/094757 CN2019094757W WO2020258359A1 WO 2020258359 A1 WO2020258359 A1 WO 2020258359A1 CN 2019094757 W CN2019094757 W CN 2019094757W WO 2020258359 A1 WO2020258359 A1 WO 2020258359A1
Authority
WO
WIPO (PCT)
Prior art keywords
tower
upflow
wastewater
neutralization
degassing
Prior art date
Application number
PCT/CN2019/094757
Other languages
English (en)
French (fr)
Inventor
杨崎峰
朱红祥
陈国宁
宋海农
陆立海
覃延定
刘熹
陈永利
林宏飞
陈倩伶
王景龙
Original Assignee
广西博世科环保科技股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广西博世科环保科技股份有限公司 filed Critical 广西博世科环保科技股份有限公司
Priority to US16/964,559 priority Critical patent/US11926549B2/en
Publication of WO2020258359A1 publication Critical patent/WO2020258359A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • 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
    • C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5281—Installations for water purification using chemical agents
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • 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
    • C02F2305/026—Fenton's reagent

Definitions

  • the invention relates to an organic wastewater treatment method, in particular to an enhanced upflow multiphase wastewater oxidation treatment process and treatment system.
  • the current technologies for the treatment of refractory wastewater include ozone oxidation, activated carbon adsorption, Fenton oxidation, etc.
  • Fenton oxidation H 2 O 2 /Fe 2+
  • H 2 O 2 /Fe 2+ is the most efficient, simple and economical method.
  • Fenton reagent The combination of ferrous salt (such as ferrous sulfate) and hydrogen peroxide (hydrogen peroxide) is called Fenton reagent, which can effectively oxidize and remove refractory organic matter that cannot be removed by traditional wastewater treatment technology.
  • the essence is H 2 O 2 in Fe 2+ Under the catalyzed action of, a hydroxyl radical ( ⁇ OH) with high reactivity is generated, and ⁇ OH can react with most organic substances to degrade it.
  • the Fenton method is a technology that uses catalysts or electrochemistry to produce OH through H 2 O 2 to treat organic matter.
  • the pure Fenton oxidation process requires a large amount of Fe 2+ to maintain sufficient ⁇ OH production, and a large amount of iron sludge is produced during the treatment process, which requires additional treatment costs.
  • Traditional homogeneous Fenton has a lot of iron sludge and has low oxidation efficiency; traditional heterogeneous Fenton has a large loss of catalyst, and the newly produced iron sludge adheres to multiple metals in the process of production and processing to combine to form a catalyst, resulting in a decrease in catalyst efficiency.
  • the technical problem to be solved by the present invention is to provide an enhanced upflow multiphase wastewater oxidation treatment process and treatment system.
  • the treatment process combines homogeneous catalysis technology, carrier heterogeneous catalysis technology, and ozone aeration catalysis technology to fully catalyze Fenton During the reaction process, the residual hydrogen peroxide is used to degrade the residual organic matter for a second time, which strengthens the processing capacity of the traditional up-flow multiphase wastewater treatment system.
  • the present invention strengthens the upflow multiphase wastewater oxidation treatment process, including the following operation steps:
  • Oxidation treatment The refractory organic wastewater is sent to an upflow multiphase wastewater oxidation system, which includes an upflow multiphase wastewater oxidation tower, in which Fenton reagents, homogeneous catalysis promoters and heterogeneous catalysis are added Carrier
  • Solid-liquid separation treatment the wastewater after oxidation treatment is sent to the solid-liquid separation system for solid-liquid separation treatment, and the separated liquid is sent to the neutralization and degassing system, and at the same time, the separated liquid is covered in the oxidation tower
  • the heterogeneous catalytic carrier of the membrane is sent back to the oxidation tower to achieve the function of enriching the catalyst;
  • the waste water treated by the solid-liquid separation system is sent to the neutralization and degassing system.
  • the neutralization and degassing system includes a connected neutralization tower and a degassing tower.
  • the wastewater is first in the neutralization tower Mix with the added lye to adjust the pH of the wastewater to 5.5-7.5, and then stir and degas in the degassing tower;
  • the neutralized and degassed wastewater is sent to the flocculation sedimentation system for mud-water separation.
  • the flocculation sedimentation system includes a flocculation sedimentation tank. After the wastewater is flocculated and sedimented, the upper supernatant of the flocculation sedimentation tank is discharged outside. The iron mud at the bottom of the flocculation sedimentation tank is filtered and transported out for harmless treatment.
  • the dosage of Fenton's reagent is added according to the conventional requirements, and the heterogeneous catalytic carrier is added before the system starts, and the dosage is 1/10 ⁇ 1/ of the volume of the upstream multiphase wastewater oxidation tower. 3.
  • the homogeneous catalytic accelerator is a liquid homogeneous catalytic accelerator, which contains trace elements of iron, manganese, cobalt, and nickel, wherein the concentration of iron is 10-20 mg/L and the concentration of manganese is 5.0-15 mg/L , The concentration of cobalt is 1.0 ⁇ 3.0mg/L, and the concentration of nickel is 0.5 ⁇ 1.0mg/L.
  • the heterogeneous catalytic carrier adopts a spherical heterogeneous catalytic carrier with a diameter of 2 to 5 mm or a polyhedral heterogeneous catalytic carrier with a maximum diagonal distance of 2 to 5 mm.
  • the material is ceramic, silica or active oxidation.
  • step 1) during the operation of the upstream multi-phase wastewater oxidation system, when the homogeneous catalytic accelerator is first dosed, it is dosed according to 1 to 5 ⁇ of the treated water volume, and the volume is maintained for 5 to 10 consecutive days. After each sand discharge from the system, it will continue to be maintained at 1 to 5 ⁇ of the treated water volume, and dosing will continue for 3 to 5 days.
  • step 2) the solid-liquid separation system adopts an inclined plate, an inclined tube or an arresting net for fluid arrest separation, or adopts a cyclone centrifugal separation and gravity separation separation.
  • step 3 the bottoms of the neutralization tower and the degassing tower are fed with mixed air with a mass concentration of 1%-10% ozone for aeration, stirring and gas stripping.
  • the treatment time in the neutralization tower is 15- 25min, the processing time of the degassing tower is 20-30min.
  • the treatment time of the flocculation sedimentation tank is 2 to 3 hours.
  • the treatment system adopted in the enhanced upflow multiphase wastewater oxidation treatment process of the present invention includes an upflow multiphase wastewater oxidation system, a solid-liquid separation system, a neutralization and degassing system, and a flocculation sedimentation system that are sequentially connected;
  • the upflow multiphase wastewater oxidation system includes an upflow multiphase wastewater oxidation tower.
  • the bottom of the upflow multiphase wastewater oxidation tower is equipped with a water distribution cover, the inside is filled with heterogeneous catalytic carriers, and the upper part is equipped with a solid-liquid separator.
  • the water distribution hood and the solid-liquid separator are respectively located below and above the heterogeneous catalytic carrier.
  • Above the solid-liquid separator is provided a water inlet A and a water inlet circulation tank connected to the water inlet A.
  • the water inlet circulation tank passes through the circulation pipe.
  • a circulating pump is installed on the circulating pipe, and a water outlet A is provided above the solid-liquid separator;
  • the solid-liquid separation system includes a cyclone separator.
  • the upper part of the cyclone separator is provided with a water inlet B connected to the water outlet A of the upflow multiphase wastewater oxidation tower, and the bottom is provided with a sand discharge pipe and a cyclone separator.
  • the neutralization and degassing system includes a neutralization tower and a degassing tower.
  • the bottoms of the neutralization tower and the degassing tower are respectively provided with a microporous aeration tray that can pass ozone air and pure oxygen, a neutralization tower and a degassing tower.
  • the upper part of the gas-liquid two-phase separator is provided with a gas-liquid two-phase separator.
  • the upper part of the gas-liquid two-phase separator is connected to the gas-liquid separator through a pipeline.
  • the gas-liquid separator is provided with a downcomer extending into the lower part of the tower.
  • the flocculation sedimentation system includes a flocculation sedimentation tank, which is connected with the water outlet D of the degassing tower.
  • the upper part of the flocculation sedimentation tank is provided with a supernatant discharge port, and the bottom is provided with a sludge discharge port.
  • the gas discharge ports of the gas-liquid separator are connected in parallel with two pipeline branches, one of which is connected to the manganese dioxide filler, and the other branch is connected to the intake pipe of the microporous aeration plate through a booster fan .
  • the present invention has the following beneficial effects:
  • the present invention improves the ability of the oxidation system to catalyze and degrade organics and reduces the dosage of Fenton's agent by adding homogeneous catalytic accelerators and heterogeneous catalytic carriers in the original upflow multiphase wastewater oxidation system;
  • the present invention can continuously supplement the catalytic active points on the surface of the carrier by regularly adding homogeneous catalytic promoters, and maintain the catalytic performance of heterogeneous catalysts;
  • the present invention can better trap the heterogeneous catalytic carrier in the system, so that it can continue to function;
  • the present invention uses a certain concentration of ozone to be mixed and aerated with air. While maintaining a certain amount of aeration, the passed ozone can catalytically react with the residual hydrogen peroxide in the water to cause secondary oxidation Process, improve the treatment effect of the system and reduce the residual medicine.
  • Figure 1 is a schematic diagram of the operation flow of the enhanced upflow multiphase wastewater oxidation treatment process of the present invention.
  • FIG. 2 is a schematic structural diagram of an upflow multiphase wastewater treatment oxidation tower used in the enhanced upflow multiphase wastewater oxidation treatment system of the present invention.
  • Figure 3 is a schematic structural diagram of a cyclone separator used in the enhanced upflow multiphase wastewater oxidation treatment system of the present invention.
  • FIG. 4 is a schematic diagram of the structure when the neutralization tower and the degassing tower used in the enhanced upflow multiphase wastewater oxidation treatment system of the present invention are connected.
  • Fig. 5 is a schematic structural diagram of the flocculation sedimentation tank used in the enhanced upflow multiphase wastewater oxidation treatment system of the present invention.
  • 1-upflow multiphase wastewater treatment oxidation tower 2-outlet A; 3-inlet circulation tank; 4-inlet A; 5-heterophase catalytic carrier; 6-solid-liquid separator; 7-circulation Pipe; 8-Circulating pump; 9-Water distribution cover; 10- Cyclone separator; 11- Central pipe; 12-Sand discharge pipe; 13-Neutralization tower; 14-Gas-liquid two-phase separator; 15-Gas-liquid Separator; 16-downcomer; 17-microporous aeration tray; 18-manganese dioxide filler; 19-degassing tower; 20-flocculation sedimentation tank, 21-water inlet B, 22-water outlet B, 23- Water inlet C, 24-water outlet C, 25-water inlet D, 26-water outlet D, 27-supernatant discharge port, 28-sludge discharge port, 29-booster fan.
  • the treatment system used in the treatment process of the present invention includes an upflow multiphase wastewater treatment system, a solid-liquid separation system, a neutralization degassing system, and a flocculation sedimentation system.
  • the upflow multiphase wastewater oxidation system of the present invention includes an upflow multiphase wastewater oxidation tower 1.
  • the bottom of the upflow multiphase wastewater oxidation tower 1 is provided with a water distribution cover 9, and the interior is filled with heterogeneous
  • the upper part of the catalytic carrier 5 is provided with a solid-liquid separator 6, the water distribution cover 9 and the solid-liquid separator 6 are respectively located below and above the heterogeneous catalytic carrier 5, and the solid-liquid separator 6 is provided with a water inlet A 4 and
  • the water inlet circulation tank 3 connected to the water inlet A 4, the water inlet circulation tank 3 is connected to the bottom water distribution cover 9 through the circulation pipe 7, and the circulation pump 8 is installed on the circulation pipe 7 above the solid-liquid separator 6.
  • the solid-liquid separation system includes a cyclone separator 10, and the upper part of the cyclone separator 10 is provided with a water inlet B 21 connected to the water outlet A 2 of the upflow multiphase wastewater oxidation tower 1.
  • a sand discharge pipe 12 is provided at the bottom, a central pipe 10 for conveying wastewater upward is provided inside the cyclone separator 10, and a water outlet B 22 is provided on the upper part of the central pipe 10.
  • the neutralization and degassing system includes a neutralization tower 13 and a degassing tower 19.
  • the bottoms of the neutralization tower 13 and the degassing tower 19 are respectively provided with microporous aerators that can pass ozone air and pure oxygen.
  • the upper part of the gas tray 17, the neutralization tower 13 and the degassing tower 19 are respectively provided with a gas-liquid two-phase separator 14, and the upper part of the gas-liquid two-phase separator 14 is connected to a gas-liquid separator 15 through a pipeline.
  • the lower part of the neutralization tower 13 is provided with a water inlet C 23 connected to the water outlet B 22 of the solid-liquid separation system, and the upper part of the neutralization tower 13 A water outlet C 24 located above the gas-liquid two-phase separator is provided.
  • the bottom of the degassing tower 19 is provided with a water inlet D 25 connected to the water outlet C 24.
  • the upper part of the degassing tower 19 is provided with a gas-liquid two-phase
  • the water outlet D 26 above the separator, the gas discharge port of the gas-liquid separator 15 is connected in parallel with two pipeline branches, one of which is connected to the manganese dioxide filler 18, and the other pipeline branch is pressurized
  • the fan 29 is connected to the intake pipe of the microporous aeration tray 17.
  • the flocculation sedimentation system includes a flocculation sedimentation tank 20, which is connected to the water outlet D 26 of the degassing tower 19.
  • the upper part of the flocculation sedimentation tank 20 is provided with a supernatant discharge port 27, and the bottom There is a sludge discharge port 28.
  • the refractory organic wastewater first enters the upflow multiphase wastewater oxidation system, which includes an upflow multiphase wastewater oxidation tower 1.
  • the refractory organic wastewater firstly enters the inlet water circulation tank 3 at the top of the upflow multiphase wastewater treatment oxidation tower 1 through the water inlet A 4, and the Fenton reagent composed of ferrous sulfate and H 2 O 2 is added to the inlet water circulation tank 3 and Homogeneous catalytic accelerator, the waste water is mixed with the medicament and enters the water distribution cover 9 at the bottom of the upflow multiphase waste water oxidation tower 1 through the circulation pipe 7.
  • the waste water is oxidized and then separated by the solid-liquid separator 6 for solid-liquid separation.
  • the water outlet A 2 is discharged into the next process.
  • the wastewater is first mixed with Fenton’s reagent to form highly reactive ⁇ OH and react with organic molecules to oxidize and degrade polymer organics into small molecular organics.
  • Fenton’s reagent Fully contact with the homogeneous catalyst promoter to generate more ⁇ OH to participate in the reaction; meanwhile, the metal elements in the homogeneous catalyst promoter and Fe 3+ generated by Fe 2+ and H 2 O 2 can crystallize or precipitate It is adsorbed on the surface of the heterogeneous catalytic carrier 5 in a manner to form heterogeneous catalytic particles. This part of the heterogeneous catalytic particles and the homogeneous catalytic promoter work together to improve the treatment efficiency of the oxidation system.
  • the dosage of Fenton's agent in this step is added according to the conventional requirements, and the heterogeneous catalytic carrier is added before the system starts, and the dosage is 1/10 to 1/3 of the volume of the upflow multiphase wastewater oxidation tower;
  • the heterogeneous catalytic carrier adopts a spherical heterogeneous catalytic carrier with a diameter of 2-5mm or a polyhedral heterogeneous catalytic carrier with a maximum diagonal distance of 2-5mm.
  • the material is an inorganic carrier of ceramic, silica or activated alumina, or Organic inert carrier for PVA and PVE.
  • the homogeneous catalyst promoter is a liquid homogeneous catalyst promoter, which contains but is not limited to cationic trace elements of iron, manganese, cobalt, and nickel, wherein the concentration of iron is 10-20 mg/L and the concentration of manganese is 5.0-15 mg/L , The concentration of cobalt is 1.0 ⁇ 3.0mg/L, and the concentration of nickel is 0.5 ⁇ 1.0mg/L.
  • the first dosage of homogeneous catalyst promoter is added according to 1 ⁇ 5 ⁇ of the treated water volume, and the supplementary dosage is maintained for 5 ⁇ 10 days; after that, every time the system is discharged After that, continue to maintain the supplementary dosage according to 1 ⁇ 5 ⁇ of the treated water volume, and continue to add for 3 ⁇ 5 days.
  • the wastewater treated by the upflow multiphase wastewater oxidation system is sent to a solid-liquid separation system, and the solid-liquid separation system may adopt a cyclone separator 10.
  • the effluent of the upflow multiphase wastewater oxidation tower 1 enters the cyclone separator 10 through the water outlet A 2, and part of the heterogeneous catalytic carrier 5 that flows into the cyclone separator 10 is concentrated in the cyclone separator 10 through the cyclone effect.
  • the bottom When the bottom reaches a certain amount, it can be discharged through the sand discharge pipe 12 for activation, regeneration and reuse, and the separated wastewater is discharged through the central pipe 10 and the water outlet B 24 and then enters the next process.
  • the solid-liquid separation system may adopt a sloping plate, an inclined tube or a blocking net for fluid blocking separation, and may also adopt a cyclone centrifugal separation and gravity separation separation.
  • the separated wastewater enters a neutralization and degassing system, which includes a neutralization tower 13 and a degassing tower 19 connected.
  • the wastewater first enters the neutralization tower 13, and the lye is added to the neutralization tower 13.
  • the bottom of the neutralization tower 13 is passed through the microporous aeration tray 17 and its connected intake pipe with a mass concentration of 1% ozone.
  • the treatment time is 15-25min
  • the pH value of the wastewater is adjusted to 5.5-7.5
  • the wastewater is subjected to gas-liquid separation treatment through the gas-liquid two-phase separator 14, and then the wastewater is sent to the dewatering
  • PAM solution is added to the degassing tower 19 and at the same time a mixed air containing 1% to 10% of the mass concentration of ozone is passed into the bottom of the degassing tower 19 for gas blowing.
  • the treatment time is 20 to 30 minutes, and then The wastewater is subjected to gas-liquid separation treatment through the gas-liquid two-phase separator 14, and then the wastewater is sent to the flocculation sedimentation system.
  • the gas-liquid two-phase separator 14 can collect carbon dioxide gas produced by the reaction and residual ozone gas that has not been completely reacted.
  • the gas-liquid separator 15 separates the gas-lifted wastewater mixture and residual ozone or air and pure oxygen mixture gas.
  • the gas-liquid separator 15 can be equipped with ozone concentration and air pressure monitoring devices. When the ozone concentration in the gas-liquid separator 15 is high, the mixed gas in the gas-liquid separator is transported to the neutralization tower and degassed by the booster fan 29 The bottom of the tower is aerated again, so that the remaining ozone is fully utilized, and advanced catalytic reaction occurs with hydrogen peroxide.
  • the liquid caustic soda added in the neutralization tower and the PAM solution added in the degassing tower are stirred until gas and liquid are monitored.
  • the ozone concentration and pressure in the separator do not meet the reuse requirements.
  • the mixed gas in the gas-liquid separator does not meet the reuse requirements, the mixed gas is discharged to the manganese dioxide filler 18 to absorb residual low-concentration ozone, so that the discharged mixed gas meets the emission requirements.
  • the mass transfer efficiency can be improved through microporous aeration, and the residual hydrogen peroxide in the wastewater is catalytically decomposed under the aeration of ozone to form newly formed ⁇ OH, which further reacts with the residual small molecular organic matter to achieve a secondary Oxidative degradation.
  • the fourth step is to send the wastewater treated by the neutralization and degassing system to the flocculation sedimentation system.
  • the flocculation sedimentation system includes a flocculation sedimentation tank 20.
  • the wastewater enters the flocculation sedimentation tank 20 and flocculates and sediments with the added flocculant in the tank.
  • the sedimentation sludge iron sludge
  • the sedimentation sludge is gravity-concentrated and discharged from the sludge discharge port 28, dehydrated and filtered, and then transported out for harmless treatment, and the supernatant in the upper part of the sedimentation tank is discharged through the supernatant discharge port 27 Discharge up to the standard; the treatment time of the flocculation sedimentation tank 20 is 2 to 3 hours.
  • the working principle of the enhanced upflow multiphase wastewater oxidation treatment system of the present invention is as follows:
  • the present invention introduces a liquid homogeneous catalytic accelerator containing iron ions and trace elements such as manganese, cobalt, nickel, etc. into the upflow multiphase wastewater treatment system, and periodically adds it to the oxidation system together with Fenton's reagent, and the transition metal is utilized during the reaction Dissatisfied with the electron affinity of the d orbital to the electron can catalyze and promote the migration of electrons during the Fenton reaction, and improve the reaction efficiency.
  • a spherical heterogeneous catalytic carrier with a diameter of 2-5mm or a polyhedral heterogeneous catalytic carrier with a maximum diagonal distance of 2-5mm is introduced.
  • the heterogeneous catalytic carrier is adsorbed during the process of fluidization with the distribution of water in the oxidation system.
  • the metal ions in the homogeneous catalytic accelerator added with the agent are adsorbed on the heterogeneous catalytic carrier to form a heterogeneous catalyst.
  • the catalyst will lose its activity after being covered by iron mud, but in the process of the present invention, the homogeneous catalysis accelerator that is added regularly will be continuously carried and attached to the carrier.
  • the adsorption of iron mud makes the catalyst surface always have catalytic active bodies, which solves the problem of decreased catalyst activity.
  • the present invention is specially equipped with a solid-liquid separation system, which can maximize the effect of the solid-liquid separation system.
  • the heterogeneous catalytic carrier remains in the oxidation system, reducing the frequency of carrier dosing and replacement.
  • the effluent treated by the solid-liquid separation system enters the neutralization and degassing system.
  • the traditional neutralization and degassing system mainly neutralizes the added and newly generated hydrogen ions during the Fenton reaction by adding alkali, and passes Aeration will blow off the small molecule volatile organic compounds and the remaining part of the hydrogen peroxide out of the system.
  • mixed air containing 1%-10% of the mass concentration of ozone is used to aerate the wastewater after alkali neutralization. During this process, ozone can undergo advanced oxidation reaction with the residual hydrogen peroxide in the mixed solution to release OH, degrade the residual organic pollutants, and further improve the effluent quality.
  • the effluent treated by the neutralization and degassing system enters the flocculation sedimentation tank, and the iron sludge in the flocculation sedimentation tank further undergoes flocculation and sedimentation.
  • the sedimentation sludge is gravity-concentrated and dehydrated before being transported and harmlessly treated, and the supernatant effluent reaches the standard for discharge .
  • the treatment process of the invention is used to treat the biochemical effluent of a paper mill, and the original wastewater has a COD of 365 mg/L and a chroma of 80 times.
  • the waste water is sent to the water inlet circulation tank at the top of the oxidation tower by a lift pump, and H 2 O 2 and FeSO 4 ⁇ 7H 2 O are added to the water inlet circulation tank.
  • the dosage of the two chemicals is: the mass ratio of H 2 O 2 to the COD to be treated in the wastewater is 1.5:1, that is, the dosage of H 2 O 2 is 547.5 mg/L, and the molar ratio of H 2 O 2 and Fe 2+ The ratio is 5:1, that is, the dosage of FeSO 4 ⁇ 7H 2 O is 895 mg/L.
  • the agent Before starting the treatment system, add silica crystals of uniform width with a maximum diagonal distance of 2mm according to 1/5 of the reactor volume, and add a liquid homogeneous accelerator according to 1 ⁇ of the designed treatment volume to promote liquid homogeneous catalysis
  • the agent adopts FeSO 4 , CoCl 2 , NiSO 4 and MnCl 2 salt solution dilution configuration, where the mass concentration of Fe is 10 mg/L, the mass concentration of Mn is 10 mg/L, the mass concentration of Co is 2 mg/L, and the mass of Ni The concentration is 0.5 mg/L, and it is continuously administered for 3 days.
  • the wastewater enters the cyclone separator to separate for 3 ⁇ 5min through the oxidation tower, and then enters the neutralization tower for acid-base neutralization, puts liquid caustic in the neutralization tower, adjusts the pH to 6-7.5, and neutralizes the bottom of the tower during this period Carry out ozone aeration and stirring, while ozone reacts with residual hydrogen peroxide in the wastewater and degrades some organic pollutants.
  • the residence time in this stage is 15-20min.
  • the neutralized wastewater enters the degassing tower.
  • the microporous aeration plate at the bottom of the degassing tower is filled with ozone, which is stirred and degassed for 20-30 minutes. Then, 0.05mg/L of PAM is added to form flocs.
  • the residual hydrogen peroxide in the mixed solution produces an advanced oxidation reaction while further degrading residual organic pollutants.
  • the degassed wastewater enters the flocculation sedimentation tank, and the flocculation sedimentation tank has a residence time of 2 to 3 hours for mud-water separation, the supernatant is discharged, and the precipitated iron mud is press filtered and transported for harmless treatment. After the treatment, the COD of the effluent drops to 50mg/L, and the chroma is reduced to 5 times.
  • the treatment process of the invention is used to treat the effluent of a certain starch factory biochemical wastewater, the original wastewater has a COD of 472 mg/L and a color degree of 75 times.
  • the waste water is sent to the water inlet circulation tank at the top of the oxidation tower by a lift pump, and H 2 O 2 and FeSO 4 ⁇ 7H 2 O are added to the water inlet circulation tank.
  • the dosage of the two chemicals is: the mass ratio of H 2 O 2 to the COD to be treated in the wastewater is 1.8:1, that is, the dosage of H 2 O 2 is 850 mg/L, and the molar ratio of H 2 O 2 to Fe 2+ It is 12:1, that is, the dosage of FeSO 4 ⁇ 7H 2 O is 579 mg/L.
  • heterogeneous catalytic support Before starting the treatment system, add heterogeneous catalytic support according to 1/10 of the reactor volume.
  • the heterogeneous catalytic support consists of silica crystals with a maximum diagonal distance of 2mm and activated alumina balls with a diameter of 5mm in a volume ratio of 1:3 Mixed composition, and add liquid homogeneous accelerator according to 3 ⁇ of the designed treatment water volume.
  • the liquid homogeneous catalyst accelerator is diluted with a salt solution of FeSO 4 , CoCl 2 , NiSO 4 and MnCl 2 , and the mass concentration of Fe is 10 mg /L, the mass concentration of Mn is 10mg/L, the mass concentration of Co is 2mg/L, and the mass concentration of Ni is 0.5mg/L, and the dosage is continuous for 3 days.
  • the wastewater enters the cyclone separator to separate for 3 ⁇ 5min through the oxidation tower, and then enters the neutralization tower for acid-base neutralization, and puts the liquid caustic into the neutralization tower to adjust the pH to 5.5-7.5, during which the neutralization tower Ozone aeration and stirring are carried out at the bottom.
  • the ozone reacts with the residual hydrogen peroxide in the waste water and degrades some organic pollutants.
  • the residence time at this stage is 20-25 minutes.
  • the neutralized wastewater enters the degassing tower, the microporous aeration plate at the bottom of the degassing tower is filled with ozone, and the degassing is carried out with stirring, degassing for 25-30 minutes, adding 0.05mg/L of PAM to form flocs, and mixing the ozone
  • the residual hydrogen peroxide in the liquid produces an advanced oxidation reaction, while further degrading residual organic pollutants.
  • the degassed wastewater enters the flocculation sedimentation tank, and the flocculation sedimentation tank has a residence time of 2 to 3 hours for mud-water separation, the supernatant is discharged, and the precipitated iron mud is press filtered and transported for harmless treatment. After treatment, the COD of the effluent dropped to 56mg/L, and the chromaticity was reduced to 4.5 times.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

本发明公开了一种强化上流式多相废水氧化处理工艺及处理系统，该处理系统包括依次相接的上流式多相废水氧化系统、固液分离系统、中和脱气系统和絮凝沉淀系统。该处理工艺包括如下步骤：1)废水进入上流式多相废水氧化系统进行氧化处理；2)将废水送入固液分离系统中进行固液分离，将分离出的异相催化载体送回至上流式多相废水氧化系统，将废水送入中和脱气系统；3)将废水送入中和脱气系统，调节废水pH至5.5～7.5，再进行搅拌脱气；4)将废水送入絮凝沉淀系统进行泥水分离，将上清液外排，将沉淀铁泥压滤后外运无害化处理。采用本发明工艺及系统，能提高多相废水氧化处理系统的处理效果，降低芬顿试剂用量，有效减少化学污泥的产生。

Description

强化上流式多相废水氧化处理工艺及处理系统 技术领域
本发明涉及有机废水处理方法，具体是一种强化上流式多相废水氧化处理工艺及处理系统。
背景技术
目前处理难生化降解废水的技术包括臭氧氧化法、活性碳吸附法、芬顿氧化法等，其中Fenton氧化法(H 2O 2/Fe 2+)是一种最高效、简单且经济的方法。
亚铁盐(如硫酸亚铁)和过氧化氢(双氧水)的组合称为Fenton试剂，它能有效氧化去除传统废水处理技术无法去除的难降解有机物，其实质是H 2O 2在Fe 2+的催化作用下生成具有高反应活性的羟基自由基(·OH)，·OH可与大多数有机物反应使其降解。
从广义上说，Fenton法是利用催化剂或电化学等作用，通过H 2O 2产生·OH处理有机物的技术。但单纯的Fenton氧化法过程中需要大量的Fe 2+投加量以维持足够的·OH产生，在处理过程中会产生大量铁泥，需要额外的处理费用。同时可能还存在部分极难降解有机物或残余有机物未被降解。传统均相的芬顿铁泥多，氧化效率低；传统异相芬顿的催化剂流失大，生产加工运行过程中新产生的铁泥附着多金属结合成催化剂，导致催化剂效率下降。
发明内容
本发明所要解决的技术问题提供一种强化上流式多相废水氧化处理工艺及处理系统，该处理工艺结合了均相催化技术、载体异相催化技术、臭氧曝气催化技术，充分地催化芬顿反应过程，并利用残留的双氧水二次降解残留有机物，强化了传统上流式多相废水处理系统的处理能力。
本发明以如下技术方案解决上述技术问题：
本发明强化上流式多相废水氧化处理工艺，包括如下操作步骤：
(1)氧化处理：将难降解有机废水送入上流式多相废水氧化系统，该系统包括上流式多相废水氧化塔，氧化塔内投加芬顿药剂、均相催化促进剂及异相 催化载体；
(2)固液分离处理：将经氧化处理后的废水送入固液分离系统中进行固液分离处理，将分离出的液体送入中和脱气系统，同时将分离出在氧化塔中覆膜的异相催化载体送回至氧化塔内，实现富集催化剂的作用；
(3)中和脱气处理：将固液分离系统处理后的废水送入中和脱气系统，中和脱气系统包括相连通的中和塔和脱气塔，废水先在中和塔内与投加的碱液混合，使废水pH调节至5.5～7.5，然后在脱气塔内进行搅拌脱气；
(4)絮凝沉淀处理：将中和脱气处理后的废水送入絮凝沉淀系统进行泥水分离，絮凝沉淀系统包括絮凝沉淀池，废水经絮凝沉淀后将絮凝沉淀池上部的上清液外排，将絮凝沉淀池底部的铁泥压滤后外运无害化处理。
所述步骤1)中，芬顿药剂的投加量按常规要求添加，异相催化载体在系统启动前投加，其投加量为上流式多相废水氧化塔容积的1/10～1/3。
步骤1)中，所述均相催化促进剂为液态均相催化促进剂，其含有铁、锰、钴、镍微量元素，其中铁的浓度10～20mg/L，锰的浓度5.0～15mg/L，钴的浓度1.0～3.0mg/L，镍的浓度0.5～1.0mg/L。
所述步骤1)中，异相催化载体采用直径在2～5mm的球状异相催化载体或最大对角距离为2～5mm的多面体异相催化载体，其材质为陶瓷、二氧化硅或活性氧化铝的无机载体，或者为PVA或PVE的有机惰性载体。
步骤1)中，上流式多相废水氧化系统在运行过程中，均相催化促进剂首次投加时，按照处理水量的1～5‰投加，并连续5～10天补投维持此量；此后每次系统排砂后，继续按照处理水量的1～5‰补投维持，并连续投加3～5天。
步骤2)中，所述固液分离系统采用斜板、斜管或拦阻网进行流体拦阻的分离方式，或采用旋流离心分离、重力分选分离的方式。
步骤3)中，所述中和塔和脱气塔的底部通入含有臭氧质量浓度为1％～10％的混合空气进行曝气搅拌和气体吹脱，中和塔中的处理时间为15～25min，脱气塔的处理时间为20～30min。
所述步骤4)中，絮凝沉淀池的处理时间为2～3小时。
本发明强化上流式多相废水氧化处理工艺采用的处理系统，包括依次相接的上流式多相废水氧化系统、固液分离系统、中和脱气系统和絮凝沉淀系统；
所述上流式多相废水氧化系统包括上流式多相废水氧化塔，上流式多相废水氧化塔的底部设有布水罩，内部填装有异相催化载体，上部设有固液分离器，布水罩和固液分离器分别位于异相催化载体的下方和上方，固液分离器的上方设有 进水口A以及与进水口A相连接的进水循环槽，进水循环槽经循环管与底部的布水罩相连接，该循环管上安装有循环泵，固液分离器的上方设有出水口A；
所述固液分离系统包括旋流分离器，旋流分离器的上部设有与上流式多相废水氧化塔的出水口A相连接的进水口B，底部设有排砂管，旋流分离器的内部设有向上输送废水的中心管，中心管的上部设有出水口B；
所述中和脱气系统包括中和塔和脱气塔，中和塔和脱气塔的底部分别设有可通入臭氧空气和纯氧的微孔曝气盘，中和塔和脱气塔的上部分别设有气液两相分离器，气液两相分离器的上方经管道连接气液分离器，气液分离器设有伸入塔下部的下降管，中和塔的下部设有与固液分离系统的出水口B相连接的进水口C，中和塔的上部设有位于气液两相分离器上方的出水口C，脱气塔的底部设有与出水口C相连接的进水口D，脱气塔的上部设有位于气液两相分离器上方的出水口D；
所述絮凝沉淀系统包括絮凝沉淀池，絮凝沉淀池与脱气塔的出水口D相连接，絮凝沉淀池的上部设有上清液排放口，底部设有污泥排放口。
所述气液分离器的气体排放口以并联方式连接两条管道支路，其中一条支路与二氧化锰填料器相连，另一条支路通过增压风机与微孔曝气盘的进气管连接。
本发明与现有技术相比，具有如下有益效果：
1)本发明是在原有上流式多相废水氧化系统中通过投加均相催化促进剂和异相催化载体的方式，提高氧化系统催化降解有机物的能力，减少芬顿药剂投加量；
2)本发明通过采用定期添加均相催化促进剂的方式，可以不断地补充载体表面的催化活性点，保持异相催化剂的催化性能；
3)本发明通过增加固液分离系统，可以更好地将异相催化载体截留在系统中，使其持续发挥作用；
4)本发明在中和以及脱气工序中采用一定浓度的臭氧与空气共同混曝，在维持一定曝气量的同时，通入的臭氧可以与水中残留的双氧水发生催化反应，发生二次氧化过程，提高系统的处理效果，减少药剂残留。
附图说明
图1是本发明强化上流式多相废水氧化处理工艺的操作流程示意图。
图2是本发明强化上流式多相废水氧化处理系统中采用的上流式多相废水处理氧化塔的结构示意图。
图3是本发明强化上流式多相废水氧化处理系统中采用的旋流分离器的结构示意图。
图4是本发明强化上流式多相废水氧化处理系统中采用的中和塔与脱气塔连接时的结构示意图。
图5是本发明强化上流式多相废水氧化处理系统中采用的絮凝沉淀池的结构示意图。
图中：1-上流式多相废水处理氧化塔；2-出水口A；3-进水循环槽；4-进水口A；5-异相催化载体；6-固液分离器；7-循环管；8-循环泵；9-布水罩；10-旋流分离器；11-中心管；12-排砂管；13-中和塔；14-气液两相分离器；15-气液分离器；16-下降管；17-微孔曝气盘；18-二氧化锰填料器；19-脱气塔；20-絮凝沉淀池，21-进水口B，22-出水口B，23-进水口C，24-出水口C，25-进水口D，26-出水口D，27-上清液排放口，28-污泥排放口，29-增压风机。
具体实施方式
为了更清楚地说明本发明处理工艺，下面结合附图和具体实施例对本发明的技术方案作进一步非限制性的详细描述。
如图1所示，本发明处理工艺采用的处理系统包括上流式多相废水处理系统、固液分离系统、中和脱气系统、絮凝沉淀系统。
如图2所示，本发明所述上流式多相废水氧化系统包括上流式多相废水氧化塔1，上流式多相废水氧化塔1的底部设有布水罩9，内部填装有异相催化载体5，上部设有固液分离器6，布水罩9和固液分离器6分别位于异相催化载体5的下方和上方，固液分离器6的上方设有进水口A 4以及与进水口A 4相连接的进水循环槽3，进水循环槽3经循环管7与底部的布水罩9相连接，该循环管7上安装有循环泵8，固液分离器6的上方设有出水口A 2。
如图3所示，所述固液分离系统包括旋流分离器10，旋流分离器10的上部设有与上流式多相废水氧化塔1的出水口A 2相连接的进水口B 21，底部设有排砂管12，旋流分离器10的内部设有向上输送废水的中心管10，中心管10的上部设有出水口B 22。
如图4所示，所述中和脱气系统包括中和塔13和脱气塔19，中和塔13和脱气塔19的底部分别设有可通入臭氧空气和纯氧的微孔曝气盘17，中和塔13和脱气塔19的上部分别设有气液两相分离器14，气液两相分离器14的上方经管道连接气液分离器15，气液分离器15设有伸入中和塔13和脱气塔19下部的下 降管16，中和塔13的下部设有与固液分离系统的出水口B 22相连接的进水口C 23，中和塔13的上部设有位于气液两相分离器上方的出水口C 24，脱气塔19的底部设有与出水口C 24相连接的进水口D 25，脱气塔19的上部设有位于气液两相分离器上方的出水口D 26，气液分离器15的气体排放口以并联方式连接两条管道支路，其中一条管道支路与二氧化锰填料器18相连，另一条管道支路通过增压风机29与微孔曝气盘17的进气管连接。
如图5所示，所述絮凝沉淀系统包括絮凝沉淀池20，絮凝沉淀池20与脱气塔19的出水口D 26相连接，絮凝沉淀池20的上部设有上清液排放口27，底部设有污泥排放口28。
本发明强化上流式多相废水氧化处理工艺的具体操作过程如下：
第一步，难降解有机废水首先进入上流式多相废水氧化系统，该系统包括上流式多相废水氧化塔1。难降解有机废水首先经进水口A 4进入上流式多相废水处理氧化塔1顶部的进水循环槽3，进水循环槽3内添加由硫酸亚铁和H 2O 2构成的芬顿试剂以及均相催化促进剂，废水与药剂混合后经循环管7进入上流式多相废水氧化塔1底部的布水罩9，废水经氧化处理后再经固液分离器6进行固液分离，然后由出水口A 2排出进入下一工序。
此步骤中，废水首先与芬顿试剂混合，形成具有高反应活性的·OH并与有机物分子发生反应，将高分子有机物氧化降解为小分子有机物，在系统良好的流化状态下，芬顿药剂与均相催化促进剂充分接触，在催化作用下生成更多的·OH参与反应；同时均相催化促进剂中的金属元素与Fe 2+和H 2O 2生成的Fe 3+以结晶或沉淀的方式吸附到异相催化载体5表面上，形成异相催化颗粒，这部分异相催化颗粒与均相催化促进剂共同作用，提高了氧化系统的处理效率。
该步骤所述的芬顿药剂的投加量按常规要求添加，而异相催化载体在系统启动前投加，投加量为上流式多相废水氧化塔容积的1/10～1/3；异相催化载体采用直径在2～5mm的球状异相催化载体或最大对角距离为2～5mm的多面体异相催化载体，其材质为陶瓷、二氧化硅或活性氧化铝的无机载体，或为PVA、PVE的有机惰性载体。
所述均相催化促进剂为液态均相催化促进剂，其含有但不限于铁、锰、钴、镍的阳离子微量元素，其中铁的浓度10～20mg/L、锰的浓度5.0～15mg/L、钴的浓度1.0～3.0mg/L、镍的浓度0.5～1.0mg/L。
在上流式多相废水氧化塔运行过程中，均相催化促进剂首次投加量是按照处理水量的1～5‰添加，并连续5～10天补投维持此量；此后每次系统排砂后，继 续按照处理水量的1～5‰补投维持，并连续投加3～5天。
第二步，将上流式多相废水氧化系统处理后的废水送入固液分离系统，所述固液分离系统可采用旋流分离器10。上流式多相废水氧化塔1的出水经出水口A 2进入旋流分离器10，部分流至旋流分离器10内部的异相催化载体5经过旋流作用被富集于旋流分离器10底部，达到一定数量后可通过排砂管12排出活化再生并回用，而分离出的废水经中心管10、出水口B 24排出后进入下一工序。
所述固液分离系统可以采用斜板、斜管或拦阻网进行流体拦阻的分离方式，也可以采用旋流离心分离、重力分选分离的方式。
第三步，将分离出的废水进入中和脱气系统，所述中和脱气系统包括相连接的中和塔13和脱气塔19。废水首先进入中和塔13，在中和塔13中投加碱液，同时在中和塔13的底部经微孔曝气盘17及其连接的进气管通入含有臭氧质量浓度为1％～10％的混合空气进行曝气搅拌，处理时间为15～25min，使废水pH值调节至5.5～7.5，然后经过气液两相分离器14将废水进行气液分离处理，再将废水送入脱气塔19内，脱气塔19中加入PAM溶液，同时在脱气塔19的底部通入含有臭氧质量浓度为1％～10％的混合空气进行气体吹脱，处理时间为20～30min，然后经过气液两相分离器14将废水进行气液分离处理，再将废水送入絮凝沉淀系统。
所述的气液两相分离器14可以收集反应产生的二氧化碳气体及未反应完全的残留臭氧气体。所述的气液分离器15分离气提上来的废水混合液和残留臭氧或空气、纯氧混合气体。气液分离器15上方可设置臭氧浓度及气压监测装置，当气液分离器15内臭氧浓度较高时，将气液分离器内的混合气体通过增压风机29输送至中和塔和脱气塔底部进行再次曝气，使得残余的臭氧得到充分利用，并与双氧水发生高级催化反应，同时对中和塔加入的液碱以及脱气塔加入的PAM溶液起到搅拌作用，直到监测到气液分离器内的臭氧浓度及压力不满足再次利用要求。当气液分离器内的混合气体不满足再次利用要求时，将混合气体排至二氧化锰填料器18吸收残余的低浓度臭氧，使得排出的混合气体满足排放要求。
该步骤通过微孔曝气可提高传质效率，而且废水在臭氧的曝气作用下，使其中残留的双氧水被催化分解，形成新生的·OH，进一步于残留的小分子有机物反应，实现二次氧化降解。
第四步，将经过中和脱气系统处理后的废水送入絮凝沉淀系统，絮凝沉淀系统包括絮凝沉淀池20，废水进入絮凝沉淀池20内，并与投加的絮凝剂在池内 发生絮凝沉淀，沉淀污泥(铁泥)经重力浓缩后由污泥排放口28排出来，并经脱水压滤，然后外运进行无害化处理，而沉淀池上部的上清液经上清液排放口27达标排放；絮凝沉淀池20的处理时间为2～3小时。
本发明强化上流式多相废水氧化处理系统的工作原理如下：
本发明在上流式多相废水处理系统中引入含铁离子及锰、钴、镍等微量元素的液态均相催化促进剂，通过定期与芬顿药剂一同加入氧化系统中，反应过程中过渡金属利用不满电子的d轨道对电子的亲和力可以催化和促进芬顿反应过程中电子的迁移，提高反应效率。而且引入直径在2～5mm的球状异相催化载体或最大对角距离为2～5mm的多面体异相催化载体，异相催化载体在氧化系统中随着布水流化的过程中通过吸附作用，将随药剂投加的均相催化促进剂中的金属离子吸附在异相催化载体上形成异相催化剂。虽然传统的异相催化芬顿系统中，催化剂会因为被铁泥覆盖后，失去活性，但是在本发明工艺中，定期投加的均相催化促进剂会不断的被载体和附着在载体上的铁泥吸附，使得催化剂的表层总是存在着催化活性体，解决了催化剂活性下降的问题。
为了防止异相催化载体在覆膜初期由于粒径较小，密度较小，容易被上升流带出氧化系统，本发明专门设置了固液分离系统，固液分离系统的作用可以最大限度的将异相催化载体保留在氧化系统中，降低载体投加跟换的频率。
本发明将固液分离系统处理后的出水进入中和脱气系统，传统的中和脱气系统主要是通过投加碱中和芬顿反应过程中投加的和新生成的氢离子，并通过曝气作用将小分子挥发性有机物和残余的部分双氧水吹脱出系统。而本发明工艺中，使用含有臭氧质量浓度为1％～10％的混合空气曝气搅拌经过碱中和后的废水，在此过程中臭氧可与混合液中残留的双氧水发生高级氧化反应，释放出·OH，降解残留有机污染物，进一步提高出水水质。
最后，将中和脱气系统处理后的出水进入絮凝沉淀池，絮凝沉淀池中铁泥进一步发生絮凝沉淀，沉淀污泥重力浓缩并脱水处理后进行外运无害化处理，上清液出水达标排放。
以下是本发明的应用实例：
实例1
采用本发明处理工艺对某造纸厂生化出水进行处理，原废水COD365mg/L，色度80倍。将废水由提升泵送入氧化塔顶部进水循环槽，在进水循环槽中投加H 2O 2和FeSO 4·7H 2O。两种药剂投加量为：H 2O 2与废水中待处理的COD质量 比为1.5:1，即H 2O 2投加量为547.5mg/L，H 2O 2与Fe 2+的摩尔比为5:1，即FeSO 4·7H 2O投加量为895mg/L。处理系统启动前按照反应器容积的1/5投加最大对角距离为2mm的宽度均匀的二氧化硅晶体，并按照设计处理水量的1‰投加液态均相促进剂，液态均相催化促进剂采用FeSO 4、CoCl 2、NiSO 4和MnCl 2的盐溶液稀释配置，其中Fe的质量浓度为10mg/L，Mn的质量浓度为10mg/L，Co的质量浓度为2mg/L，Ni的质量浓度为0.5mg/L，连续投加3天。
废水经氧化塔出水后进入旋流分离器分离3～5min，而后进入中和塔进行酸碱中和，在中和塔内投入液碱，调节pH至6～7.5，在此期间中和塔底部进行臭氧曝气搅拌，同时臭氧跟废水中残留的双氧水反应，并降解部分有机污染物，此阶段停留时间15～20min。经中和后的废水进入脱气塔，脱气塔底部微孔曝气盘通入臭氧，进行搅拌脱气，脱气20～30min，再加入0.05mg/L的PAM形成絮体，同时臭氧跟混合液中的残留的双氧水产生高级氧化反应，同时进一步降解残留有机污染物。脱气后的废水进入絮凝沉淀池，絮凝沉淀池停留时间2～3小时，进行泥水分离，上清液出水外排，沉淀铁泥压滤后外运无害化处理。处理后的出水COD降至50mg/L，色度降低至5倍。
实例2
采用本发明处理工艺对某淀粉厂生化废水出水进行处理，原废水COD472mg/L，色度75倍。将废水由提升泵送入氧化塔顶部进水循环槽，在进水循环槽中投加H 2O 2和FeSO 4·7H 2O。两种药剂投加量为：H 2O 2与废水中待处理的COD质量比为1.8:1，即H 2O 2投加量为850mg/L，H 2O 2与Fe 2+的摩尔比为12:1，即FeSO 4·7H 2O投加量为579mg/L。处理系统启动前按照反应器容积的1/10投加异相催化载体，异相催化载体由最大对角距离为2mm的二氧化硅晶体和直径为5mm的活性氧化铝球按照体积比1:3混合组成，并按照设计处理水量的3‰投加液态均相促进剂，液态均相催化促进剂采用FeSO 4、CoCl 2、NiSO 4和MnCl 2的盐溶液稀释配置，其中Fe的质量浓度为10mg/L，Mn的质量浓度为10mg/L，Co的质量浓度为2mg/L，Ni的质量浓度为0.5mg/L，连续投加3天。
废水经氧化塔出水后进入旋流分离器分离3～5min，而后进入中和塔进行酸碱中和，在中和塔内投入液碱，以调节pH至5.5～7.5，在此期间中和塔底部进行臭氧曝气搅拌，同时臭氧跟废水中残留的双氧水反应，并降解部分有机污染物，此阶段停留时间20～25min。经中和后的废水进入脱气塔，脱气塔底部微孔曝气盘通入臭氧，进行搅拌脱气，脱气25～30min，加入0.05mg/L的PAM形成 絮体，同时臭氧跟混合液中的残留的双氧水产生高级氧化反应，同时进一步降解残留有机污染物。脱气后的废水进入絮凝沉淀池，絮凝沉淀池停留时间2～3小时，进行泥水分离，上清液出水外排，沉淀铁泥压滤后外运无害化处理。处理后的出水COD降至56mg/L，色度降低至4.5倍。
需要指出的是，上述实施例仅为说明本发明的技术构思，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (10)

  1. 强化上流式多相废水氧化处理工艺，其特征在于，包括如下操作步骤：
    1)氧化处理：将难降解有机废水送入上流式多相废水氧化系统，该系统包括上流式多相废水氧化塔，氧化塔内投加芬顿药剂、均相催化促进剂及异相催化载体；
    2)固液分离处理：将经氧化处理后的废水送入固液分离系统中进行固液分离处理，将分离出的液体送入中和脱气系统，同时将分离出在氧化塔中覆膜的异相催化载体送回至氧化塔内，实现富集催化剂的作用；
    3)中和脱气处理：将固液分离系统处理后的废水送入中和脱气系统，中和脱气系统包括相连通的中和塔和脱气塔，废水先在中和塔内与投加的碱液混合，使废水pH调节至5.5～7.5，然后在脱气塔内进行搅拌脱气；
    4)絮凝沉淀处理：将中和脱气处理后的废水送入絮凝沉淀系统进行泥水分离，絮凝沉淀系统包括絮凝沉淀池，废水经絮凝沉淀后将絮凝沉淀池上部的上清液外排，将絮凝沉淀池底部的铁泥压滤后外运无害化处理。
  2. 根据权利要求1所述强化上流式多相废水氧化处理工艺，其特征在于，所述步骤1)中，芬顿药剂的投加量按常规要求添加，异相催化载体在系统启动前投加，其投加量为上流式多相废水氧化塔容积的1/10～1/3。
  3. 根据权利要求1所述强化上流式多相废水氧化处理工艺，其特征在于，步骤1)中，所述均相催化促进剂为液态均相催化促进剂，其含有铁、锰、钴、镍微量元素，其中铁的浓度10～20mg/L，锰的浓度5.0～15mg/L，钴的浓度1.0～3.0mg/L，镍的浓度0.5～1.0mg/L。
  4. 根据权利要求1所述强化上流式多相废水氧化处理工艺，其特征在于，所述步骤1)中，异相催化载体采用直径在2～5mm的球状异相催化载体或最大对角距离为2～5mm的多面体异相催化载体，其材质为陶瓷、二氧化硅或活性氧化铝的无机载体，或者为PVA或PVE的有机惰性载体。
  5. 根据权利要求1所述强化上流式多相废水氧化处理工艺，其特征在于，步骤1)中，上流式多相废水氧化系统在运行过程中，均相催化促进剂首次投加量是按照处理水量的1～5‰投加，并连续5～10天补投维持此量；此后每次系统排 砂后，继续按照处理水量的1～5‰补投维持，并连续投加3～5天。
  6. 根据权利要求1所述强化上流式多相废水氧化处理工艺，其特征在于，步骤2)中，所述固液分离系统采用斜板、斜管或拦阻网进行流体拦阻的分离方式，或采用旋流离心分离、重力分选分离的方式。
  7. 根据权利要求1所述强化上流式多相废水氧化处理工艺，其特征在于，步骤3)中，所述中和塔和脱气塔的底部通入含有臭氧质量浓度为1％～10％的混合空气进行曝气搅拌和气体吹脱，中和塔中的处理时间为15～25min，脱气塔的处理时间为20～30min。
  8. 根据权利要求1所述强化上流式多相废水氧化处理工艺，其特征在于，所述步骤4)中，所述絮凝沉淀池的处理时间为2～3小时。
  9. 根据权利要求1至8任一所述强化上流式多相废水氧化处理工艺采用的处理系统，其特征在于，包括依次相接的上流式多相废水氧化系统、固液分离系统、中和脱气系统和絮凝沉淀系统；
    所述上流式多相废水氧化系统包括上流式多相废水氧化塔(1)，上流式多相废水氧化塔的底部设有布水罩(9)，内部填装有异相催化载体(5)，上部设有固液分离器(6)，布水罩(9)和固液分离器(6)分别位于异相催化载体(5)的下方和上方，固液分离器(6)的上方设有进水口A(4)以及与进水口A相连接的进水循环槽(3)，进水循环槽经循环管(7)与底部的布水罩相连接，该循环管上安装有循环泵(8)，固液分离器的上方设有出水口A(2)；
    所述固液分离系统包括旋流分离器(10)，旋流分离器的上部设有与上流式多相废水氧化塔的出水口A(2)相连接的进水口B(21)，底部设有排砂管(12)，旋流分离器(10)的内部设有向上输送废水的中心管(11)，中心管(11)的上部设有出水口B(22)；
    所述中和脱气系统包括中和塔(13)和脱气塔(19)，中和塔和脱气塔的底部分别设有可通入臭氧空气和纯氧的微孔曝气盘(17)，中和塔和脱气塔的上部分别设有气液两相分离器(14)，气液两相分离器的上方经管道连接气液分离器(15)，气液分离器(15)设有伸入塔下部的下降管(16)，中和塔的下部设有与固液分离系统的出水口B(22)相连接的进水口C(23)，中和塔的上部设有位于气液两相分离器上方的出水口C(24)，脱气塔的底部设有与出水口C(24)相连接的进水口D(25)，脱气塔的上部设有位于气液两相分离器上方的出水口D(26)；
    所述絮凝沉淀系统包括絮凝沉淀池(20)，絮凝沉淀池(20)与脱气塔的出 水口D(26)相连接，絮凝沉淀池(20)的上部设有上清液排放口(27)，底部设有污泥排放口(28)。
  10. 根据权利要求9所述强化上流式多相废水氧化处理工艺采用的处理系统，其特征在于，所述气液分离器(15)的气体排放口以并联方式连接两条管道支路，其中一条支路与二氧化锰填料器(18)相连，另一条支路通过增压风机(29)与微孔曝气盘(17)的进气管连接。
PCT/CN2019/094757 2019-06-21 2019-07-04 强化上流式多相废水氧化处理工艺及处理系统 WO2020258359A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/964,559 US11926549B2 (en) 2019-06-21 2019-07-04 Treatment process and treatment system of enhanced up-flow multiphase wastewater oxidation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910551143.4A CN110316861A (zh) 2019-06-24 2019-06-24 强化上流式多相废水氧化处理工艺及处理系统
CN201910551143.4 2019-06-24

Publications (1)

Publication Number Publication Date
WO2020258359A1 true WO2020258359A1 (zh) 2020-12-30

Family

ID=68120138

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/094757 WO2020258359A1 (zh) 2019-06-21 2019-07-04 强化上流式多相废水氧化处理工艺及处理系统

Country Status (2)

Country Link
CN (1) CN110316861A (zh)
WO (1) WO2020258359A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111018187A (zh) * 2019-12-25 2020-04-17 苏州希图环保科技有限公司 基于芬顿氧化反应的废水处理工艺

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101519251A (zh) * 2009-04-09 2009-09-02 广西大学 上流式多相氧化塔处理难生化降解废水工艺
EP2500323A1 (en) * 2011-03-14 2012-09-19 E' Cosi' S.R.L. Method for the degradation of industrial wastewater and apparatus for performing the method
CN105884154A (zh) * 2016-06-29 2016-08-24 盐城工学院 一种处理化工废水的新型组合工艺
CN106882866A (zh) * 2017-02-24 2017-06-23 河北科技大学 双氧水协同臭氧非均相催化氧化处理废水的方法
KR20180006842A (ko) * 2017-06-05 2018-01-19 유흥케미칼(주) 산업부산물 유래 황산철 용액을 이용한 폐수처리 방법
CN108191039A (zh) * 2018-02-24 2018-06-22 武汉纺织大学 一种高效复合型芬顿试剂及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN202924850U (zh) * 2012-11-28 2013-05-08 北京市环境保护科学研究院 一种污水高级氧化系统
JP2014198286A (ja) * 2013-03-29 2014-10-23 栗田工業株式会社 難生物分解性有機物含有水の処理方法及び処理装置
CN108373237B (zh) * 2018-03-23 2020-09-22 大连大学 一种农药生产废水的处理装置
CN210764696U (zh) * 2019-06-24 2020-06-16 广西博世科环保科技股份有限公司 强化上流式多相废水氧化处理系统

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101519251A (zh) * 2009-04-09 2009-09-02 广西大学 上流式多相氧化塔处理难生化降解废水工艺
EP2500323A1 (en) * 2011-03-14 2012-09-19 E' Cosi' S.R.L. Method for the degradation of industrial wastewater and apparatus for performing the method
CN105884154A (zh) * 2016-06-29 2016-08-24 盐城工学院 一种处理化工废水的新型组合工艺
CN106882866A (zh) * 2017-02-24 2017-06-23 河北科技大学 双氧水协同臭氧非均相催化氧化处理废水的方法
KR20180006842A (ko) * 2017-06-05 2018-01-19 유흥케미칼(주) 산업부산물 유래 황산철 용액을 이용한 폐수처리 방법
CN108191039A (zh) * 2018-02-24 2018-06-22 武汉纺织大学 一种高效复合型芬顿试剂及其制备方法

Also Published As

Publication number Publication date
CN110316861A (zh) 2019-10-11

Similar Documents

Publication Publication Date Title
US11926549B2 (en) Treatment process and treatment system of enhanced up-flow multiphase wastewater oxidation
CN114684948B (zh) 一种Fenton流化床处理废水的工艺方法和工艺系统
CN212293233U (zh) 一种低浓度难降解化工废水处理系统
WO2023140319A1 (ja) 工業廃水の処理システム、工業廃水の処理システムの使用、工業廃水の処理方法、及び廃水処理プロセス
CN113735245A (zh) 一种臭氧催化氧化污水的方法
CN102040262B (zh) 一种流化床电解催化氧化反应装置和处理方法
CN210764696U (zh) 强化上流式多相废水氧化处理系统
CN208916960U (zh) 一种芬顿氧化装置
WO2020258359A1 (zh) 强化上流式多相废水氧化处理工艺及处理系统
CN117566952A (zh) 一种芬顿法深度处理废水的系统和方法
CN111762969A (zh) 一种低浓度难降解化工废水处理方法及系统
KR101964756B1 (ko) 개선된 반송 구조를 갖는 악취제거 미생물을 이용한 고농도 유기폐수의 처리장치
CN116143352A (zh) 一种垃圾渗滤液全量化组合处理系统及其处理方法
CN110436710A (zh) 一种尼龙6生产废水高效处理装置及处理工艺
CN116119888A (zh) 一种垃圾渗滤液膜后浓缩液组合处理系统及处理方法
CN212222726U (zh) 一种垃圾渗滤液处理系统
CN208907056U (zh) 一种半流化床式芬顿氧化废水处理装置
CN113184996A (zh) 基于自控的一体式自养脱氮耦合生物除磷的方法及装置
CN112047466A (zh) 一种废水中硫酸盐、亚硝酸盐和有机物的一体式去除装置及方法
CN111138044A (zh) 一种垃圾渗滤液处理系统
CN211847316U (zh) 一种新型芬顿氧化装置
CN109455796B (zh) 一种零价铁内电解耦合内循环流化床Fenton的工业废水处理工艺
CN214735187U (zh) 一种垃圾渗滤液的处理装置
CN215048978U (zh) 一种臭氧催化氧化污水的装置
CN108516649A (zh) 提高煤气化制乙二醇污水脱氮率的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19934639

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19934639

Country of ref document: EP

Kind code of ref document: A1