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CN-121974522-A - Wastewater treatment method adopting ceramic ultrafiltration membrane composite oxidation adsorption

CN121974522ACN 121974522 ACN121974522 ACN 121974522ACN-121974522-A

Abstract

A wastewater treatment method by ceramic ultrafiltration membrane composite oxidation adsorption comprises the steps of sequentially passing wastewater to be treated through a ceramic ultrafiltration membrane filtration unit, an oxidation reaction unit and an adsorption purification unit. Wherein the average pore diameter of the ceramic ultrafiltration membrane is 10-50nm, the transmembrane pressure difference is 0.15-0.4MPa, the membrane surface flow rate is 1.5-4.5m/s, the high-efficiency solid-liquid separation is realized, the ultrafiltration produced water enters an oxidation reaction unit, the ultrafiltration produced water is catalyzed and oxidized with ozone and/or hydrogen peroxide under the action of a supported catalyst, the ozone addition amount is 40-100mg/L, the oxidized effluent is deeply purified by a modified activated carbon adsorption column, and the empty bed flow rate is 10-18BV/h. The oxidation unit and the adsorption unit can be further integrated to form a series integrated reaction column. The system has the functions of concentrated solution circulation oxidation, gas-water combined backwashing, chemical enhanced cleaning and on-line monitoring and automatic control. The invention can effectively remove refractory organic matters and heavy metals, has stable operation and excellent effluent quality, and is suitable for advanced treatment of high-concentration industrial wastewater.

Inventors

  • Hua Xianyan

Assignees

  • 杰纳(苏州)环保设备有限公司

Dates

Publication Date
20260505
Application Date
20260224
Priority Date
20251223

Claims (10)

  1. 1. The wastewater treatment method for ceramic ultrafiltration membrane composite oxidation adsorption is characterized by comprising the following steps: the wastewater to be treated sequentially passes through a ceramic ultrafiltration membrane filtering unit, an oxidation reaction unit and an adsorption purification unit; Performing solid-liquid separation in the ceramic ultrafiltration membrane filtration unit by adopting a tubular ceramic ultrafiltration membrane with an average pore diameter of 10-50nm, and operating a transmembrane pressure difference of 0.15-0.4MPa and a membrane surface flow rate of 1.5-4.5m/s to obtain ultrafiltration produced water and concentrated solution; introducing the ultrafiltration water into an oxidation reaction unit, and carrying out catalytic oxidation reaction with ozone and/or hydrogen peroxide in the presence of a supported catalyst; And (3) introducing the oxidized effluent into an adsorption purification unit, and deeply removing residual pollutants through a modified adsorption material to obtain purified effluent.
  2. 2. The wastewater treatment method of ceramic ultrafiltration membrane composite oxidation adsorption according to claim 1, wherein the ceramic ultrafiltration membrane is made of the following materials Compounding or compounding Compounding, wherein the inner diameter of the support body is 6-10mm, the thickness of the membrane layer is 15-30 mu m, and the pure water flux is 500-1200L +. The operation temperature is 20-55 ℃.
  3. 3. The wastewater treatment method of ceramic ultrafiltration membrane composite oxidation adsorption according to claim 1, wherein the oxidation reaction unit adopts an external fixed bed reactor, and the catalyst is Or (b) The modified particle carrier has a dry-base filling amount of 350-550g/L, an ozone adding amount of 40-100mg/L, a hydrogen peroxide adding amount of 10-40mg/L, a volume ratio of ozone tail gas to liquid of 6-10:1, a reaction pH of 6.8-8.2 and a hydraulic retention time of 18-35min.
  4. 4. The wastewater treatment method of ceramic ultrafiltration membrane composite oxidation adsorption according to claim 1, wherein the adsorption purification unit adopts a fixed bed adsorption column, is filled with modified coconut activated carbon or coal columnar activated carbon, has a particle size of 0.8-1.2mm, an iodine value of 1200-1400mg/g, and a specific surface area The contact time of the empty bed is 4-8min, and the flow rate of the running empty bed is 10-18BV/h.
  5. 5. The wastewater treatment method of ceramic ultrafiltration membrane composite oxidation adsorption according to claim 1, wherein the oxidation reaction unit and the adsorption purification unit are integrated to form a series integrated reaction column, a catalytic oxidation zone (height 0.5-0.8 m) and an adsorption zone (height 1.2-1.8 m) are sequentially arranged in the column from bottom to top, the compound mole ratio of ozone to hydrogen peroxide is 1:0.4-1:0.6, and the total residence time is 20-30min.
  6. 6. The wastewater treatment method for ceramic ultrafiltration membrane composite oxidation adsorption according to claim 1, wherein the ceramic ultrafiltration membrane filtration unit adopts gas-water combined backwash in combination with chemical enhanced backwash, and backwash gas strength is 9-11L- Backwash water strength 18-22L- The backwashing period is 8-20h, the chemical enhanced backwashing adopts 0.6-0.9wt% NaOH+300-450 mg/L NaClO mixed solution, the temperature is 55-62 ℃, and the soaking time is 40-50min.
  7. 7. The wastewater treatment method of ceramic ultrafiltration membrane composite oxidation adsorption according to any one of claims 1 to 6, wherein the system is equipped with sensors for monitoring transmembrane pressure difference, ORP, TOC and pH on line, and when transmembrane pressure difference is not less than 0.35MPa or ORP is lower than a set value, ozone addition is automatically increased by 15 to 20% or membrane chemical cleaning procedure is started.
  8. 8. The wastewater treatment method for ceramic ultrafiltration membrane composite oxidation adsorption according to any one of claims 1 to 6, wherein concentrated solution generated by the ceramic ultrafiltration membrane is returned to the oxidation reaction unit for cyclic catalytic oxidation, the cyclic multiplying power is 4 to 7 times, and the concentrated solution after cyclic treatment enters the subsequent concentration or solidification unit.
  9. 9. The wastewater treatment method adopting ceramic ultrafiltration membrane composite oxidation adsorption according to any one of claims 1 to 6, wherein the ceramic ultrafiltration membrane filtration unit is operated in a constant flux mode, and the flux is controlled to be 80-250L- And the rotation speed of the water inlet pump is regulated through frequency conversion to maintain the stability of the transmembrane pressure difference.
  10. 10. The wastewater treatment method for ceramic ultrafiltration membrane composite oxidation adsorption according to any one of claims 1 to 6, wherein the ozone is added through a titanium alloy microporous aeration disc or a venturi jet device, the average diameter of bubbles is less than or equal to 800 μm, and the gas-liquid mass transfer efficiency is more than or equal to 85%.

Description

Wastewater treatment method adopting ceramic ultrafiltration membrane composite oxidation adsorption Technical Field The invention belongs to the technical field of advanced treatment of industrial wastewater, and particularly relates to a wastewater treatment method by ceramic ultrafiltration membrane composite oxidation adsorption. Background Along with the increasingly strict environmental protection standards, the wastewater produced in the industries of chemical industry, printing and dyeing industry, coal chemical industry, pharmacy, coking industry and the like has the characteristics of COD (Chemical Oxygen Demand) high, large chroma, hard-degradation organic matters and heavy metals, strong biotoxicity, poor biodegradability and the like. The traditional physicochemical and biochemical technology is difficult to stably reach the first grade A or more surface water environment quality standard of pollutant emission standard of urban sewage treatment plant (GB 18918-2002). In recent years, ceramic ultrafiltration membranes are widely applied to pretreatment and advanced treatment of high-difficulty industrial wastewater due to the advantages of acid and alkali resistance, high temperature resistance, oxidation resistance, strong pollution resistance, high mechanical strength, long service life and the like, but only solid-liquid separation can be realized by a single ceramic membrane, and soluble organic pollutants cannot be effectively removed. Advanced oxidation techniques (AOPs) can produce strong oxidizing propertiesThe degradation of the organic matters which are difficult to degrade, but the single use has the risks of low utilization rate of the oxidant, high running cost, possibility of generating secondary pollutants such as bromate and the like. Although the activated carbon adsorption can deeply remove residual organic matters and heavy metals, the problems of high adsorption saturation, difficult regeneration and the like exist. Most of the prior patent and literature reports are a simple series process of ceramic membrane and single oxidation or oxidation and common adsorption, and the following defects exist: 1. Each unit is arranged independently, so that the occupied area is large, the pipeline connection is complex, and the operation energy consumption is high; 2. The ceramic membrane is easy to be polluted by organic matters and colloid, the cleaning frequency is high, and the flux attenuation is fast; 3. the oxidation section and the adsorption section lack of cooperative optimization, so that the residual oxidant is easy to cause the early failure of the adsorbent; 4. the concentrated solution is not effectively recycled or subjected to harmless treatment, and the risk of secondary pollution exists. Therefore, a new method for treating wastewater, which is capable of separating ceramic ultrafiltration membrane, catalyzing, oxidizing, adsorbing and purifying deeply and has the functions of system integration, automatic control and concentrated solution circulation treatment, is needed to realize stable, low-cost and high-efficiency deep purification. Disclosure of Invention In order to overcome the defects of easy pollution of a ceramic ultrafiltration membrane, low utilization rate of an oxidant, easy saturation and failure of an adsorbent, poor cooperativity of each treatment unit, difficult innocent treatment of concentrated solution, large system occupation area, high operation cost and the like in the prior advanced treatment technology of industrial wastewater, the invention aims to provide a wastewater treatment method of ceramic ultrafiltration membrane composite oxidation adsorption, which is optimized by the separation of the ceramic ultrafiltration membrane, the advanced coupling of catalytic oxidation and adsorption purification and the system integration, the method realizes the grading and high-efficiency removal of refractory organics, heavy metals and colloids, obviously slows down membrane pollution, improves the synergistic efficiency of an oxidation and adsorption unit, prolongs the service life of materials, realizes the cyclic mineralization and near zero emission of concentrated solution, and finally achieves the overall technical effects of stable operation, high degree of automation, excellent effluent quality and low comprehensive treatment cost, and meets the severe emission standard or recycling requirement. In order to achieve the above purpose, the invention provides a wastewater treatment method by ceramic ultrafiltration membrane composite oxidation adsorption, which comprises the following steps: the wastewater to be treated sequentially passes through a ceramic ultrafiltration membrane filtering unit, an oxidation reaction unit and an adsorption purification unit; Performing solid-liquid separation in the ceramic ultrafiltration membrane filtration unit by adopting a tubular ceramic ultrafiltration membrane with an average pore diameter of 10-50nm,