CN105174418A - Method for treating oil-containing sewage in refined oil depot by catalytic oxidation - Google Patents

Method for treating oil-containing sewage in refined oil depot by catalytic oxidation Download PDF

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Publication number
CN105174418A
CN105174418A CN201510670664.3A CN201510670664A CN105174418A CN 105174418 A CN105174418 A CN 105174418A CN 201510670664 A CN201510670664 A CN 201510670664A CN 105174418 A CN105174418 A CN 105174418A
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CN
China
Prior art keywords
catalyzer
water
catalyst
catalytic oxidation
oil
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Pending
Application number
CN201510670664.3A
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Chinese (zh)
Inventor
牟桂琴
张宏哲
唐晓丽
张志远
郭亚逢
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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Priority to CN201510670664.3A priority Critical patent/CN105174418A/en
Publication of CN105174418A publication Critical patent/CN105174418A/en
Pending legal-status Critical Current

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Abstract

The invention relates to a method for treating oil-containing sewage in a refined oil depot by catalytic oxidation, and mainly solves the problem of lower removal rate in the prior art. The method for treating the oil-containing sewage in the refined oil depot by catalytic oxidation comprises the following steps of adding sodium chlorate and hydrochloric acid into the oil-containing sewage in the refined oil depot, stirring for 2-20 minutes, generating chlorine dioxide, then adding a catalyst, and treating for 20-180 minutes, wherein the catalyst is a copper-based active carbon catalyst; copper oxide serving as an active component is supported on an active carbon carrier; the weight percentage of the metal active component is 0.5-8.0 percent; the adding amount of sodium chlorate is 1.0-3.0g/L, and the adding amount of the catalyst is 0.5-1g/L; the adjusted pH value of hydrochloric acid is 1-6. According to the technical scheme, the problem is better solved; the method can be used in treatment of the oil-containing sewage in the refined oil depot.

Description

The method of catalytic oxidation treatment product oil storage field oily(waste)water
Technical field
The present invention relates to a kind of method of catalytic oxidation treatment product oil storage field oily(waste)water.
Background technology
Product oil storage field oily(waste)water, except containing except mechanical impurity, suspension oil, dispersed oil and oil in water emulsion, also has dissolving oil, methyl tertiary butyl ether etc., complicated component, and after air-flotation process, chemical oxygen demand COD is usually at more than 2000mg/L, and ordinary method is difficult to process.
CN201310565057.1 discloses a kind for the treatment of process of oily(waste)water.The method comprises the steps: 1) initial filter: tentatively filtered by filter screen by oily(waste)water, filter residue enters rubbish container, and the oily(waste)water after filtration enters apparatus for treating sewage; 2) in apparatus for treating sewage, sewage-treating agent is added, and add pH adjusting agent and regulate the pH value of sewage to 6.5-7.5, sewage-treating agent is made up of bodied ferric sulfate, Sodium salts humic acids, polyacrylamide, and the consumption of bodied ferric sulfate, Sodium salts humic acids, polyacrylamide is respectively 0.6-1.2mg/L, 1.0-1.6mg/L, 40-50mg/L; 3) react 2-4h after adding sewage-treating agent, by the oil reservoir sucking-off of apparatus for treating sewage upper surface, lower floor's sewage is discharged.
Sodium chlorate oxidizing power in neutral or weakly alkaline solution is very low, but in an acidic solution or when having induced oxidation agent and catalyzer (as copper sulfate) to exist, is then strong oxidizer.Act on acids (as sulfuric acid) and release dioxide peroxide, have extremely strong oxidizing power.
Dioxide peroxide is as the strongest strong oxidizer of oxidisability in chlorine system oxygenant, and oneself is widely used in field of Environment Protection by people in recent years, but the past uses as sterilizing agent and water purification agent because they are costly many, uses not extensive in wastewater treatment.Be oxygenant with dioxide peroxide at normal temperatures and pressures, take transition metal as catalyzer, the intermediate product that the organic chemical contaminant oxygenolysis in aqueous phase is compared with readily biodegradable or comparatively easily removing, its cost can reduce greatly, economically creates condition for sodium chlorate application in the treatment of waste water.Therefore, be equipped with suitable catalyzer in conjunction with itself oxidisability aspect superiority, ClO 2 catalyzed oxidation will have wide future in process used water difficult to degradate.
Summary of the invention
Technical problem to be solved by this invention is the problem that in prior art, clearance is lower, provides a kind of method of new catalytic oxidation treatment product oil storage field oily(waste)water.The method is used for, in product oil storage field oily water treatment, having the advantage that clearance is higher.
For solving the problem, the technical solution used in the present invention is as follows: a kind of method of catalytic oxidation treatment product oil storage field oily(waste)water, first in product oil storage field oily(waste)water, sodium chlorate, hydrochloric acid is added, stir process 2-20 minute, generate dioxide peroxide, then catalyzer is added, process 20-90 minute; Wherein, catalyzer is copper-based active Pd/carbon catalyst, is that active ingredient is supported on absorbent charcoal carrier with cupric oxide, wherein the weight percentage of metal active constituent is 0.5-8%, sodium chlorate add-on is 0.2-1.0g/L, and catalyzer is 0.5-1g/L, and hydrochloric acid adjusted to ph is 1.0-6.0.
In technique scheme, preferably, the preparation process of described catalyzer is: support of the catalyst is washed till neutrality with distilled water by (1), then under 80-120 DEG C of condition, dries 6-12 hour, for subsequent use after dry; (2) by Cu (NO 3) 2be dissolved in distilled water and obtain steeping fluid, then dried gac is immersed in the Cu (NO of preparation 3) 2flood 12-24 hour in steeping fluid, then vacuum filtration, after naturally drying, put into loft drier, dry 6-12 hour until dry under regulating loft drier temperature to 80-120 DEG C of condition; (4) be placed in retort furnace by dried gac, regulate muffle furnace to 350-450 DEG C, by catalyzer roasting 3-12 hour, roasting terminates rear obtained required catalyzer.
This patent provides a kind of method utilizing sodium chlorate catalytic oxidation treatment product oil storage field oily(waste)water, because product oil storage field oily(waste)water is except containing except mechanical impurity, suspension oil, dispersed oil and oil in water emulsion, also have dissolving oil, methyl tertiary butyl ether etc., complicated component, after air-flotation process, COD is usually at more than 2000mg/L.Because Pollutant levels are high, toxicity is large, and biodegradability is poor again, biochemical process can not be adopted to process, and absorption method exists the high problem of running cost, and ordinary method is difficult to process.Sodium chlorate can produce dioxide peroxide in acid condition, and under catalyzer existent condition, COD degradation rate reaches more than 90%, can reach the object to product oil storage field oily(waste)water qualified discharge, achieves good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Reaction times is to product oil storage field oily water treatment effect.
This experiment only adds sodium chlorate and processes sewage, the process water yield is 200mL, entering water COD is that 2105 (this enters water is the water outlet of product oil storage field oily(waste)water after oil removal, air supporting, in air supporting process, add sewage-treating agent: bodied ferric sulfate, Sodium salts humic acids, polyacrylamide.), sodium chlorate add-on is 0.2g, and pH value is 6, and result is as shown in table 1.
Table 1
Reaction times (min) Water outlet COD (mg/L) Clearance (%)
20 1607 24
60 1320 37
90 1243 41
[embodiment 2]
This effects pH is to product oil storage field oily water treatment effect.
This experiment adds sodium chlorate, hydrochloric acid processes sewage, and the process water yield is 200mL, and entering water COD is 2105mg/L, and sodium chlorate add-on is 0.2g, and the reaction times is 60 minutes, and result is as shown in table 2.
Table 2
pH Water outlet COD (mg/L) Clearance (%)
6.0 1320 37
3.2 1214 42
1.3 1073 49
[embodiment 3]
Catalyst levels is to product oil storage field oily water treatment effect.
This experiment adds sodium chlorate, hydrochloric acid, catalyzer process sewage, and the process water yield is 200mL, and entering water COD is 2105mg/L, and sodium chlorate add-on is 0.2g, and pH value is 1.3, and the reaction times is 60 minutes.
The preparation method of catalyzer is: (1) weighs in the balance and gets 5g activated char catalyst carrier and with distilled water, support of the catalyst be washed till neutrality, then dries 2 hours under 100 DEG C of conditions, for subsequent use after dry;
(2) weigh in the balance and get 6gCu (NO 3) 2, be dissolved in obtained steeping fluid in 50mL distilled water; After dried gac is immersed in prepared Cu (NO 3) 2dipping 24 hours in steeping fluid (mass concentration 4%), then vacuumizing filtration;
(3) it is dried naturally, then put into loft drier, dry 2 hours until dry at regulating loft drier temperature to 100 DEG C;
(4) be placed in retort furnace by dried gac, regulate muffle furnace to 400 DEG C, by catalyzer roasting 4 hours, roasting terminated rear obtained finished catalyst.
Table 3
Catalyst levels (g) Water outlet COD (mg/L) Clearance (%)
0.05 337 84
0.1 136 94
0.2 116 94
[embodiment 4]
Sodium chlorate is to product oil storage field oily water treatment effect.
This experiment adds sodium chlorate, hydrochloric acid, catalyzer process sewage, and the process water yield is 200mL, and entering water COD is 2105mg/L, and catalyst charge is 0.2g, and pH value is 1.3, and the reaction times is 60 minutes.
Table 3
Sodium chlorate consumption (g) Water outlet COD (mg/L) Clearance (%)
0.04 851 60
0.1 321 85
0.2 116 94

Claims (2)

1. a method for catalytic oxidation treatment product oil storage field oily(waste)water, first adds sodium chlorate, hydrochloric acid, stir process 2-20 minute in product oil storage field oily(waste)water, generates dioxide peroxide, then adds catalyzer, process 20-180 minute; Wherein, catalyzer is copper-based active Pd/carbon catalyst, is that active ingredient is supported on absorbent charcoal carrier with cupric oxide, wherein the weight percentage of metal active constituent is 0.5-8%, sodium chlorate add-on is 1.0-3.0g/L, and catalyzer is 0.5-1.0g/L, and hydrochloric acid adjusted to ph is 1.0-6.0.
2. the method for catalytic oxidation treatment product oil storage field oily(waste)water according to claim 1, it is characterized in that the preparation process of described catalyzer is: support of the catalyst is washed till neutrality with distilled water by (1), then under 80-120 DEG C of condition, 6-12 hour is dried, for subsequent use after dry; (2) by Cu (NO 3) 2be dissolved in distilled water and obtain steeping fluid, then dried gac is immersed in the Cu (NO of preparation 3) 2flood 12-24 hour in steeping fluid, then vacuum filtration, after naturally drying, put into loft drier, dry 6-12 hour until dry under regulating loft drier temperature to 80-120 DEG C of condition; (4) be placed in retort furnace by dried gac, regulate muffle furnace to 350-450 DEG C, by catalyzer roasting 3-12 hour, roasting terminates rear obtained required catalyzer.
CN201510670664.3A 2015-10-13 2015-10-13 Method for treating oil-containing sewage in refined oil depot by catalytic oxidation Pending CN105174418A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114890638A (en) * 2022-06-02 2022-08-12 洛阳昊海环保科技有限公司 Resource utilization method of oil-and organic-containing Fenton iron mud
CN115010238A (en) * 2022-06-23 2022-09-06 天津市创嘉生物技术有限公司 Water purifying agent and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN101116827A (en) * 2006-07-31 2008-02-06 中国石油化工股份有限公司 Catalyzer for preparing low carbon olefinic hydrocarbon through hydrocarbons catalytic oxidation cracking
US7985709B2 (en) * 2002-01-22 2011-07-26 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts
CN102451713A (en) * 2010-10-15 2012-05-16 中国石油化工股份有限公司 Catalyst for treating industrial wastewater, and preparation method thereof

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US7985709B2 (en) * 2002-01-22 2011-07-26 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts
CN101116827A (en) * 2006-07-31 2008-02-06 中国石油化工股份有限公司 Catalyzer for preparing low carbon olefinic hydrocarbon through hydrocarbons catalytic oxidation cracking
CN102451713A (en) * 2010-10-15 2012-05-16 中国石油化工股份有限公司 Catalyst for treating industrial wastewater, and preparation method thereof

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项玉婷: "高COD含油污水处理技术研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114890638A (en) * 2022-06-02 2022-08-12 洛阳昊海环保科技有限公司 Resource utilization method of oil-and organic-containing Fenton iron mud
CN115010238A (en) * 2022-06-23 2022-09-06 天津市创嘉生物技术有限公司 Water purifying agent and preparation method thereof

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