CN102689976A - Application of water-soluble phthalocyanine catalyst in treating semi-coke wastewater - Google Patents
Application of water-soluble phthalocyanine catalyst in treating semi-coke wastewater Download PDFInfo
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- CN102689976A CN102689976A CN2012102058421A CN201210205842A CN102689976A CN 102689976 A CN102689976 A CN 102689976A CN 2012102058421 A CN2012102058421 A CN 2012102058421A CN 201210205842 A CN201210205842 A CN 201210205842A CN 102689976 A CN102689976 A CN 102689976A
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- phthalocyanine
- catalyzer
- water
- waste water
- blue charcoal
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Abstract
The invention relates to the field of environmental engineering, particularly application of a water-soluble phthalocyanine catalyst in treating semi-coke wastewater. The invention is characterized by comprising the following steps: introducing industrial oxygen into semi-coke wastewater; and adding 0.05-0.2 g/L water-soluble phthalocyanine to react at 60-300 DEG C under the oxygen partial pressure of 0.5-2.5 MPa under the condition of pH 7-8 for 90-180 minutes. The COD (chemical oxygen demand) removal rate is up to 50-90%, and the BOD5 (biochemical oxygen demand)/CODcr is 0.5-0.9. The water-soluble phthalocyanine catalyst is a phthalocyanine metal sulfonate catalyst or carboxyl-substituted phthalocyanine metal catalyst. Compared with the prior art, the invention greatly enhances the catalytic wet oxidation reaction efficiency, and greatly improves the biodegradability of the treated wastewater; and by combining further biochemical treatment or advanced treatment, the invention can further enhances the effluent water quality, so that the semi-coke wastewater is discharged after achieving the standard or is recycled.
Description
Technical field
The present invention relates to adopt in the environmental engineering technical field of catalytic wet air oxidation treatment of high concentration, indegradable industrial effluent, relate in particular to the application of a kind of water soluble metal phthalocyanine catalyzer in handling blue charcoal waste water.
Background technology
To be a kind of lump coal by middle low metamorphic grade produce the trade effluent that produces in blue charcoal (the coke a kind of) process in middle low-temperature pyrolysis to blue charcoal waste water; Its water-quality constituents is very complicated; Wherein the COD composition is main with heteroaromatic hydro carbons and senior assorted first aldehydes matter; COD is up to 20000～50000mg/L, and intractability is very big.This high density, indegradable industrial effluent; Can not directly use biochemical process handles; And adopting physics and the direct processing cost of chemical process high, present representative technology is to be that the sewage incineration technology of thermal source is handled blue charcoal waste water with coal gas, but a large amount of energy (coal gas) of this Technology Need consumption; Water outlet after the processing is discharged with gaseous form, and heat and water all can not carry out reuse.
Orchid charcoal manufacturing enterprise is mostly in China's western (Shaanxi, the Inner Mongol, Gansu, Ningxia, Xinjiang one band) lack of water and ecosystem vulnerable area; The pollution of blue charcoal waste water brings huge pressure for the sustainable development of enterprise and local ecotope; Research and develop new wastewater processing technology and be used to reduce blue charcoal waste water COD; And improve its biodegradability, imperative.The CWO technology provides a kind of effective novel treatment technology for the organic waste water of high density difficult for biological degradation; It is meant in high temperature, high pressure, liquid phase with oxygen or air as oxygenant; Under the effect of catalyzer, making the organic waste water selective oxidation is CO
2, H
2O, N
2A kind of treatment process Deng innoxious substance.
In the similar technology of Xi'an Technology University, adopt immersion process for preparing Catalysts Cu O/ γ-Al
2O
3, be index with waste water COD cr clearance, investigated of the influence of Cu charge capacity to catalytic activity; Secondly,, select to have added the second active ingredient Mn and structural promoter Ce, prepared Catalysts Cu O-MnO in order to improve activity of such catalysts and stability
2-CeO
2/ γ-Al
2O
3, and confirmed the optimum reaction condition under the laboratory condition: temperature of reaction is 150 ℃, and oxygen partial pressure is that 1.6 MPa, stirring velocity are 500 r/min, and water inlet pH value is 8.With this understanding, react 2 h after, the CODcr clearance is 77.8%, chroma removal rate reaches 80.6%.
Summary of the invention
The objective of the invention is to propose the application of a kind of water soluble metal phthalocyanine catalyzer in handling blue charcoal waste water; The water soluble metal phthalocyanine catalyzer that has high catalytic activity through use; Reduction is to the requirement of reaction conditions; Shorten the reaction times, to the removal efficient of pollutent, improve the biodegradability of blue charcoal waste water in the raising CWO reaction process.
For solving the problems of the technologies described above, technical scheme of the present invention is:
The application of water soluble metal phthalocyanine catalyzer in handling blue charcoal waste water; In blue charcoal waste water, feed industrial oxygen; In temperature of reaction is that 60～300 ℃, oxygen partial pressure are that 0.5～2.5Mpa, pH are under 7～8 the condition, adds water soluble metal phthalocyanine catalyzer 0.05～0.2g/L, behind reaction 90～180min; The COD clearance reaches 50～90%, BOD
5/ COD
Cr0.5～0.9.
Said industrial oxygen and the volume ratio of blue charcoal waste water under standard state are: (1.13～5.65): 1.
Said water soluble metal phthalocyanine catalyzer is phthalocyanine metal Sulfonates catalyzer or carboxyl substituted phthalocyanine metal catalyzer, and such catalyzer thermostability and chemicalstability are all fine, and electronic structure is induced transition of electron easily, and catalytic performance is excellent.
The mechanism of action of water soluble metal phthalocyanine catalyzer in the CWO reaction process is to be adsorbed with organic pollutants on the one hand; OH, RO ROOCO have been promoted on the other hand
2, H
2O, N
2, inorganic salt etc., when the COD of blue charcoal waste water value scope during at 25000～40000mg/L, COD removal can reach 50～90%.Said phthalocyanine metal Sulfonates catalyzer is a kind of in CuPc ammonium sulphonate, FePC ammonium sulphonate, Phthalocyanine Zinc ammonium sulphonate and the phthalocyanine cobalt ammonium sulphonate.Said carboxyl substituted phthalocyanine metal catalyzer is a kind of in carboxyl substituted CuPc, carboxyl substituted FePC, carboxyl substituted Phthalocyanine Zinc and the carboxyl substituted phthalocyanine cobalt.
Compared with prior art, the invention has the beneficial effects as follows:
1) adopt water miscible phthalocyanine metal Sulfonates catalyzer with high catalytic activity and carboxyl substituted phthalocyanine metal catalyzer as catalyzer; Not only improved the CWO reaction efficiency significantly; And the biodegradability of processed waste water increases substantially; In conjunction with further biochemical treatment or advanced treatment, further improve effluent characteristics, can make blue charcoal waste water realize qualified discharge or recycle.
2) the COD clearance of processed waste water can reach 50～90% (when not adding catalyzer, clearance is 28%), and the organic concentration in the waste water greatly reduces, and bio-toxicity is greatly improved, and its BOD
5/ COD
CrBring up to 0.5～0.9 from 0.2 and (work as BOD
5/ COD
Cr, show that the biodegradability of waste water is good at＞0.3 o'clock), the short chain carboxy acid of formation has biodegradability preferably, makes the biochemical treatment of follow-up routine become possibility.
Embodiment
Below in conjunction with specific embodiment the present invention is described further:
Adopt catalytic wet air oxidation to handle blue charcoal waste water among embodiment 1～embodiment 12 respectively, to different phthalocyanine metal Sulfonates catalyst and reaction condition, concrete process conditions see Table 1 with the processing comparing result.
Adopt catalytic wet air oxidation to handle blue charcoal waste water among embodiment 13～embodiment 24 respectively, to different carboxyl substituted phthalocyanine metal catalyst and reaction condition, concrete process conditions see Table 2 with the processing comparing result.
The blue charcoal waste water of table 1 phthalocyanine metal Sulfonates catalyst treatment result contrast
The blue charcoal waste water of table 2 carboxyl substituted phthalocyanine metal catalyst treatment result contrast
Claims (5)
1. the application of water soluble metal phthalocyanine catalyzer in handling blue charcoal waste water; It is characterized in that, in blue charcoal waste water, feed industrial oxygen, is that 60～300 ℃, oxygen partial pressure are that 0.5～2.5Mpa, pH are under 7～8 the condition in temperature of reaction; Add water soluble metal phthalocyanine catalyzer 0.05～0.2g/L; Behind reaction 90～180min, the COD clearance reaches 50～90%, BOD
5/ COD
Cr0.5～0.9.
2. the application of water soluble metal phthalocyanine catalyzer according to claim 1 in handling blue charcoal waste water is characterized in that said industrial oxygen and the volume ratio of blue charcoal waste water under standard state are: (1.13～5.65): 1.
3. the application of water soluble metal phthalocyanine catalyzer according to claim 1 in handling blue charcoal waste water is characterized in that said water soluble metal phthalocyanine catalyzer is phthalocyanine metal Sulfonates catalyzer or carboxyl substituted phthalocyanine metal catalyzer.
4. the application of water soluble metal phthalocyanine catalyzer according to claim 3 in handling blue charcoal waste water; It is characterized in that said phthalocyanine metal Sulfonates catalyzer is a kind of in CuPc ammonium sulphonate, FePC ammonium sulphonate, Phthalocyanine Zinc ammonium sulphonate and the phthalocyanine cobalt ammonium sulphonate.
5. the application of water soluble metal phthalocyanine catalyzer according to claim 3 in handling blue charcoal waste water; It is characterized in that said carboxyl substituted phthalocyanine metal catalyzer is a kind of in carboxyl substituted CuPc, carboxyl substituted FePC, carboxyl substituted Phthalocyanine Zinc and the carboxyl substituted phthalocyanine cobalt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102058421A CN102689976A (en) | 2012-06-20 | 2012-06-20 | Application of water-soluble phthalocyanine catalyst in treating semi-coke wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102058421A CN102689976A (en) | 2012-06-20 | 2012-06-20 | Application of water-soluble phthalocyanine catalyst in treating semi-coke wastewater |
Publications (1)
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|---|---|
| CN102689976A true CN102689976A (en) | 2012-09-26 |
Family
ID=46855735
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|---|---|---|---|
| CN2012102058421A Pending CN102689976A (en) | 2012-06-20 | 2012-06-20 | Application of water-soluble phthalocyanine catalyst in treating semi-coke wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880242A (en) * | 2014-03-13 | 2014-06-25 | 中钢集团鞍山热能研究院有限公司 | Advanced treatment process of coal chemical industry wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5207927A (en) * | 1992-03-18 | 1993-05-04 | Uop | Treatment of an aqueous stream containing water-soluble inorganic sulfide compounds |
| CN1403459A (en) * | 2001-08-24 | 2003-03-19 | 中国石油天然气股份有限公司 | Prepn of oxidizing and desulfurizing catalyst phthalocyanine cobalt sulfonate |
| CN101855175A (en) * | 2007-09-10 | 2010-10-06 | 梅里凯姆公司 | Removal of residual sulfur compounds from a caustic stream |
-
2012
- 2012-06-20 CN CN2012102058421A patent/CN102689976A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5207927A (en) * | 1992-03-18 | 1993-05-04 | Uop | Treatment of an aqueous stream containing water-soluble inorganic sulfide compounds |
| CN1403459A (en) * | 2001-08-24 | 2003-03-19 | 中国石油天然气股份有限公司 | Prepn of oxidizing and desulfurizing catalyst phthalocyanine cobalt sulfonate |
| CN101855175A (en) * | 2007-09-10 | 2010-10-06 | 梅里凯姆公司 | Removal of residual sulfur compounds from a caustic stream |
Non-Patent Citations (1)
| Title |
|---|
| 张彩凤 等: "催化湿式氧化处理兰炭废水的工艺研究", 《山东化工》, vol. 40, no. 4, 15 April 2011 (2011-04-15) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880242A (en) * | 2014-03-13 | 2014-06-25 | 中钢集团鞍山热能研究院有限公司 | Advanced treatment process of coal chemical industry wastewater |
| CN103880242B (en) * | 2014-03-13 | 2015-09-30 | 中钢集团鞍山热能研究院有限公司 | A kind of coal chemical industrial waste water advanced treatment process |
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Application publication date: 20120926 |