Method for treating wastewater with high hydroxybenzene contained through catalyzing wet oxidation

Abstract

A process for treating the phenol contained sewage by catalytic wet oxidizing method features that its catalyst is prepared from the active component chosen from Pt, Pd, Rh and Ru, the auxiliary component chosen from La, Ce, Pr and Nd, and TiO2-ZrO2 carrier through baking at 60-180 deg.C for 2-18 hrs and calcining at 300-800 deg.c for 2-18 hrs. It is applied under the conditions: 220-280 deg.C for reaction temp, 4-8 MPa for pressure, 50-300 for air / water ratio, and 0.5-6 / hr for space speed. Its advantages are high reaction efficiency, high removal rate of COD up to 99%, and high BOD5 / CODcr increased from 0.02 to 0.6.

Description

technical field

[0001] The invention relates to the treatment of high-phenol-containing wastewater, in particular to a method for catalytic wet oxidation treatment of high-phenol-containing wastewater. The process of the present invention is also suitable for treating other similar high-concentration and refractory industrial organic wastewater. Background technique

[0002] The wastewater produced in the production of phenolic resin, explosives, rubber and other chemical processes not only has a high COD value, but also contains a large amount of phenolic substances. Denaturation, high concentration can cause protein precipitation; phenol has direct damage to various cells, and has a strong corrosive effect on skin and mucous membranes; in addition, phenol has a great impact on aquatic organisms, and low concentration phenol pollutes water, which can affect fish When the concentration is high, a large number of fish can be killed; the use of phenolic wastewater to irrigate...

Examples

Embodiment 1

[0015] Catalyst PR-2

[0016] Preparation of catalyst PR-2: 20g of TiSO 4 and an equal amount of ZrSO 4 Dissolve in 500ml of distilled water, and after it is completely dissolved, add 1M NaOH solution dropwise until the pH value is 10. Then filter, and wash the resulting precipitate repeatedly until the SO in the washing liquid 4 2- and Na + The concentration of the filter cake is less than 0.1ppm, and the resulting filter cake is extruded; then dried at 120°C for 12 hours, and then roasted at 600°C for 12 hours, using the TiO-ZrO prepared above as a carrier, using The equal-volume impregnation method impregnates the main active components Pt, Pd and auxiliary components La and Ce respectively, wherein Pt2%, Pd1% and La1%, Ce1% are loaded. Then dry at 60 and 120°C for 12 hours, and finally bake at 550°C for 8 hours to obtain catalyst PR-2;

[0017] Utilizing Catalytic Wet Oxidation Technology to Treat the Phenolic Resin Wastewater

[0018] The COD value of the wastewate...

Embodiment 2

[0020] Catalyst PR-2

[0021] The preparation method of catalyst PR-2 is the same as "Example 1".

[0022] Utilizing Catalytic Wet Oxidation Technology to Treat the Phenolic Resin Wastewater

[0023] The COD value of the wastewater is 17333mg / l, the pH is 6, at 6.6MPa, 260°C, and the space velocity is 1.33 -1 , Gas / H 2 Under the reaction condition of O(volume)=130, using catalyst PR, after catalytic wet oxidation treatment, the COD value of wastewater is 458mg / l, pH is 7, and the removal rate of COD is 97.4%. The content of free phenol in wastewater was reduced from 0.746% before treatment to no detection after treatment; and its BOD 5 / COD cr From less than 0.02 to greater than 0.6, this kind of wastewater can be treated by the combined technology of catalytic wet oxidation and biological oxidation, and the treated wastewater can reach the discharge standard.

Embodiment 3

[0025] Catalyst RN-1

[0026] Preparation of catalyst RN-1: The preparation method of carrier TiO-ZrO is the same as that in Example 1. The main active components Rh, Ru and auxiliary components Pr, Nd were respectively impregnated by the method of equal volume impregnation, wherein Rh0.2%, Ru4% and Pr3.5%, Nd0.3%. Then respectively at 60 and 120 Dry at ℃ for 12 hours, and finally bake at 550℃ for 8 hours to obtain catalyst RN-1;

[0027] Utilizing Catalytic Wet Oxidation Technology to Treat the Phenolic Resin Wastewater

[0028] The COD value of the wastewater is 21589mg / l, and the pH is 6. At 6.6MPa, 260°C, and the space velocity is 1.0 -1 , Gas / H 2 Under the reaction condition of O (body)=130, adopt catalyst RN-1, after catalytic wet oxidation process, the COD value of waste water is 522mg / l, and pH is 7, and the removal rate of COD is 97.5%; Free phenol in waste water The content was reduced from 0.746% before treatment to no detection after treatment; and its BOD 5 / ...

technical field

[0001] The invention relates to the treatment of high-phenol-containing wastewater, in particular to a method for catalytic wet oxidation treatment of high-phenol-containing wastewater. The process of the present invention is also suitable for treating other similar high-concentration and refractory industrial organic wastewater. Background technique

[0002] The wastewater produced in the production of phenolic resin, explosives, rubber and other chemical processes not only has a high COD value, but also contains a large amount of phenolic substances. Denaturation, high concentration can cause protein precipitation; phenol has direct damage to various cells, and has a strong corrosive effect on skin and mucous membranes; in addition, phenol has a great impact on aquatic organisms, and low concentration phenol pollutes water, which can affect fish When the concentration is high, a large number of fish can be killed; the use of phenolic wastewater to irrigate...

Examples

Embodiment 1

[0015] Catalyst PR-2

[0016] Preparation of catalyst PR-2: 20g of TiSO 4 and an equal amount of ZrSO 4 Dissolve in 500ml of distilled water, and after it is completely dissolved, add 1M NaOH solution dropwise until the pH value is 10. Then filter, and wash the resulting precipitate repeatedly until the SO in the washing liquid 4 2- and Na + The concentration of the filter cake is less than 0.1ppm, and the resulting filter cake is extruded; then dried at 120°C for 12 hours, and then roasted at 600°C for 12 hours, using the TiO-ZrO prepared above as a carrier, using The equal-volume impregnation method impregnates the main active components Pt, Pd and auxiliary components La and Ce respectively, wherein Pt2%, Pd1% and La1%, Ce1% are loaded. Then dry at 60 and 120°C for 12 hours, and finally bake at 550°C for 8 hours to obtain catalyst PR-2;

[0017] Utilizing Catalytic Wet Oxidation Technology to Treat the Phenolic Resin Wastewater

[0018] The COD value of the wastewate...

Embodiment 2

[0020] Catalyst PR-2

[0021] The preparation method of catalyst PR-2 is the same as "Example 1".

[0022] Utilizing Catalytic Wet Oxidation Technology to Treat the Phenolic Resin Wastewater

[0023] The COD value of the wastewater is 17333mg / l, the pH is 6, at 6.6MPa, 260°C, and the space velocity is 1.33 -1 , Gas / H 2 Under the reaction condition of O(volume)=130, using catalyst PR, after catalytic wet oxidation treatment, the COD value of wastewater is 458mg / l, pH is 7, and the removal rate of COD is 97.4%. The content of free phenol in wastewater was reduced from 0.746% before treatment to no detection after treatment; and its BOD 5 / COD cr From less than 0.02 to greater than 0.6, this kind of wastewater can be treated by the combined technology of catalytic wet oxidation and biological oxidation, and the treated wastewater can reach the discharge standard.

Embodiment 3

[0025] Catalyst RN-1

[0026] Preparation of catalyst RN-1: The preparation method of carrier TiO-ZrO is the same as that in Example 1. The main active components Rh, Ru and auxiliary components Pr, Nd were respectively impregnated by the method of equal volume impregnation, wherein Rh0.2%, Ru4% and Pr3.5%, Nd0.3%. Then respectively at 60 and 120 Dry at ℃ for 12 hours, and finally bake at 550℃ for 8 hours to obtain catalyst RN-1;

[0027] Utilizing Catalytic Wet Oxidation Technology to Treat the Phenolic Resin Wastewater

[0028] The COD value of the wastewater is 21589mg / l, and the pH is 6. At 6.6MPa, 260°C, and the space velocity is 1.0 -1 , Gas / H 2 Under the reaction condition of O (body)=130, adopt catalyst RN-1, after catalytic wet oxidation process, the COD value of waste water is 522mg / l, and pH is 7, and the removal rate of COD is 97.5%; Free phenol in waste water The content was reduced from 0.746% before treatment to no detection after treatment; and its BOD 5 / ...