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A method for treating reverse osmosis concentrated water by catalytic oxidation using heterogeneous Fenton reaction

A reverse osmosis concentrated water, catalytic oxidation technology, applied in the direction of oxidized water/sewage treatment, chemical instruments and methods, chemical/physical processes, etc., can solve the problems of catalyst loss, reduced treatment effect, low utilization efficiency, etc., to reduce COD value and chromaticity, process is easy to control, and the effect of stable and standard discharge

Active Publication Date: 2019-02-15
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Chinese patent CN201210199491.8 discloses a method for treating coking wastewater by flocculation-FeOOH combined process. In this patent, FeOOH is used to generate hydroxyl radicals to oxidize and degrade organic pollutants in coking wastewater, but FeOOH cannot be recycled, and in acidic conditions Fe 2+ Dissolution reduces the oxidation effect; in addition, the flocculation process is not suitable for the treatment of petrochemical wastewater with low suspended solids, high salt content, and high organic pollutants
CN201210587397.X discloses a heterogeneous Fenton reagent and its preparation method and the method of using heterogeneous Fenton reagent to carry out wet oxidation to remove NO in flue gas. In this patent, the catalyst is supported by iron salt on active Al 2 o 3 It is prepared on the surface, and the pH of the solution is required to be 5 to 6 during the wet oxidation process, which limits the scope of use of the heterogeneous Fenton reagent. If it is applied to a wastewater system with a pH value 2 o 2 The amount used is 0.5~1.5mol / L, resulting in H 2 o 2 Lower utilization efficiency and higher processing costs

Method used

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  • A method for treating reverse osmosis concentrated water by catalytic oxidation using heterogeneous Fenton reaction
  • A method for treating reverse osmosis concentrated water by catalytic oxidation using heterogeneous Fenton reaction
  • A method for treating reverse osmosis concentrated water by catalytic oxidation using heterogeneous Fenton reaction

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Experimental program
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Embodiment 1

[0037] The preparation method of the supported transition metal oxide catalyst is as follows: 1) Carrier pretreatment: add 1.0% silica sol by mass percentage to 200 mesh powdered activated carbon, rotationally mold, dry at 100°C for 24h, and obtain a diameter of 2.0-4.0mm 2) catalyst preparation: ①, weigh 27.80g FeSO 4 ·7H 2 O, 3.75g CuSO 4 ·5H 2 O, 3.23g CoCl 2 ·6H 2 O, 1.97gMnSO 4 ·H 2 0, add 1000mL distilled water, make it dissolve fully under stirring; Nitrogen is exposed to the mixed solution for 20min; 0.005 times, the pH value of the solution was adjusted to 9.0 with ammonia water, and the solution gradually changed from yellow-green to dark green; ③. Place 20.0 g of the pretreated carrier in the cathode area of ​​the electrolytic cell, and then add the complexed mixed solution In the electrolytic cell, the cathode and anode of the electrolytic cell are spectrally pure graphite electrodes; ④. Place the electrolytic cell in a water bath, control the temperature at...

Embodiment 2

[0044] The preparation method of the supported transition metal oxide catalyst is as follows: 1) Carrier pretreatment: add 1.5% silica sol by mass percentage to 250 mesh powdered activated carbon, rotate molding, and dry at 100°C for 22 hours to obtain a diameter of 1.0-3.0mm 2) Catalyst preparation: ①, weigh 29.81g FeCl 2 4H 2 O, 7.32gCu(NO 3 ) 2 ·3H 2 O, 6.15gCoSO 4 ·7H 2 O, 5.86gMn(NO 3 ) 2 4H 2 0, add 1000mL distilled water, stir to make it fully dissolved; nitrogen exposure to the mixed solution for 30min; ②, add complexing agent sodium citrate aqueous solution to the mixed solution, the molar number of complexing agent is 0.0075 of the molar number of ferrous chloride times, the pH value of the solution was adjusted to 8.5 with ammonia water, and the solution gradually changed from yellow-green to dark green; ③, 25.0 g of the pretreated carrier was placed in the cathode area of ​​the electrolytic cell, and then the complexed mixed solution was added to the In th...

Embodiment 3

[0050] The preparation method of the supported transition metal oxide catalyst is as follows: 1) Carrier pretreatment: adding 2.0% silica sol by mass percentage into 300 mesh molecular sieve MCM-41, rotating molding, drying at 90°C for 20h, and obtaining a 2.5mm spherical particles for standby; 2) Catalyst preparation: ①, weigh 37.43gFe(NO 3 ) 2 ·6H 2 O, 4.92gCuSO 4 ·5H 2 O, 4.68gCoCl 2 ·6H 2 O, 5.13gMn(NO 3 ) 2 4H 2 0, add 1000mL distilled water, stir to make it fully dissolved; Nitrogen is exposed to the mixed solution for 25min; ②, add the aqueous solution of complexing agent to the mixed solution, the complexing agent is a mixture of ethylenediaminetetraacetic acid and sodium fluoride (mass Ratio 1:1:), the number of moles of the complexing agent is 0.006 times the number of moles of ferrous nitrate, the pH value of the solution is adjusted to 9.0 with ammonia water, and the solution gradually changes from yellow-green to dark green; ③, pretreated carrier 25.0g is p...

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Abstract

The invention discloses a method for treating reverse osmosis (RO) concentrated water through heterogeneous Fenton-like reaction catalytic oxidization and belongs to the technical field of environment protection. In the method, a supported transition metal oxide is employed as a Fenton-like reaction catalyst, wherein an active component of the catalyst is a mixture of transition metals comprising, by mass, 60-80% of Fe, 10-15% of Cu, 3-13% of Co and 7-12% of Mn. In the presence of the Fenton-like reaction catalyst and H2O2, a reaction is carried out with the RO concentrated water, wherein the organic pollutants in the RO concentrated water is oxidized and degraded through a generated hydroxyl free radical in a non-selective manner. The method is simple in processes, is convenient to carry out and is simple in process control. The catalyst can be recycled, so that the method is economical and available, can reduce COD value and chroma in the RO concentrated water high-effectively and quickly within a wide pH value range (3.0-8.0) without secondary pollution. The method achieves stable and standardized emission of the RO concentrated water, and has excellent promoting prospect.

Description

technical field [0001] The invention belongs to the technical field of waste water treatment, and in particular relates to a method for treating petrochemical reverse osmosis concentrated water by using heterogeneous Fenton-like reaction catalytic oxidation. Background technique [0002] Reverse osmosis technology is an advanced and effective membrane separation technology, which is widely used in the advanced treatment of wastewater in petrochemical enterprises, but the concentrated reverse osmosis water produced during the operation of the reverse osmosis device has the following characteristics: (1) COD (chemical Oxygen demand) value is high, generally above 120mg / L, mainly some refractory organic pollutants; 2. High chroma, generally between 50 and 1500 times; 3. Poor biodegradability, organic matter in concentrated water is mainly It is a refractory organic pollutant, generally BOD / COD<0.1, so it is difficult for organic matter in concentrated water to participate in...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C02F1/72B01J23/889
Inventor 李常青刘发强杨岳刘光利江岩巫树锋梁宝锋曹凤霞王军何琳贾媛媛张媛文善雄李扬李晶蕊荣树茂周霞
Owner PETROCHINA CO LTD
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