CN109019962A - A kind of processing method of refinery alkaline sewage - Google Patents

A kind of processing method of refinery alkaline sewage Download PDF

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Publication number
CN109019962A
CN109019962A CN201810933149.3A CN201810933149A CN109019962A CN 109019962 A CN109019962 A CN 109019962A CN 201810933149 A CN201810933149 A CN 201810933149A CN 109019962 A CN109019962 A CN 109019962A
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cod
alkaline sewage
refinery alkaline
refinery
concentration ratio
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高伟杰
李秀
祖建锁
韩大为
张树德
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NORENDAR INTERNATIONAL Ltd
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NORENDAR INTERNATIONAL Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/026Fenton's reagent

Abstract

The present invention relates to a kind of processing methods of refinery alkaline sewage comprising following steps: (1) pH for adjusting refinery alkaline sewage is 2 ~ 8;(2) Fenton oxidation: mass concentration ratio H is carried out to refinery alkaline sewage2O2/ COD=0.5 ~ 5.0, mass concentration ratio H2O2/Fe2+=20,10 ~ 30min of reaction time;(3) pH of waste water is to neutrality;(4) waste water is centrifuged, and revolution is 1000 r/min;(5) waste water carries out activated carbon adsorption: active carbon dosage 10 ~ 50g/L, pH are 6 ~ 8, and adsorption time is 1 ~ 4 hour.The present invention is directed to refinery alkaline sewage high concentration, feature difficult to degrade and poisonous and harmful, refinery alkaline sewage is after Fenton reagent aoxidizes, activated carbon adsorption is carried out, water outlet meets first discharge standard as defined in national " urban wastewater treatment firm pollutant emission standard (GB18918-2002) ".

Description

A kind of processing method of refinery alkaline sewage
Technical field
The present invention relates to technical field of waste water processing, and in particular to a kind of processing method of refinery alkaline sewage.
Background technique
By in the products such as gasoline, diesel oil, kerosene impurity or undesirable ingredient removal, to improve the processing of oil quality Process is known as oil refinery process.The method of oil refinery mainly has caustic washing electric refining and hydrofinishing.Currently, each refining in China Oily factory is few using hydrofinishing, and what is generallyd use is improvement technique-alkali cleaning electrochemistry essence of early stage acid-alkali refining method System.This method has the advantages that treatment process is simple, cost is relatively low, can recycle Major organic species;Primary disadvantage is that row Refinery alkaline sewage concentration height out is difficult to degrade, if direct emission or processing are discharged not up to standard can cause to natural environment seriously Pollution.
Refinery alkaline residue is broadly divided into according to the difference in source: the line refinery of Chang Yi, two, three alkaline residue, refinery diesel alkaline residue, refining Change gasoline alkaline residue, liquid hydrocarbon refinery alkaline residue etc..Refinery alkaline sewage is mostly brown, milky or grey black, and has effluvium Dilute mucus of taste also contains in the alkaline residue from different process in addition to the free alkali containing various concentration, neutral oil and aphthenic acids The substances such as a large amount of sulfide, mercaptan, thioether and creosote.
Refinery alkaline sewage belongs to high concentration, difficult to degrade, poisonous and hazardous extraordinary organic chemical waste water.Since its height contains Sulphur, high the features such as containing phenol, high COD, stench and strong corrosive, have been put into National Hazard waste register.According to petrochemical industry Sewage Water Emissions primary standard (GB4281-84) regulation: petrochemical plant and plant effuent Treatment stations discharge outlet water pollutant Highest allows concentration of emission to be respectively as follows: pH value 6 ~ 9, sulfide 1mg/L, volatile phenol 0.5mg/L, petroleum-type 10mg/L, COD200mg/L。
Sulfide and phenols in refinery alkaline sewage are major pollutants and stench source.Sulfide is to organism in water system It unites toxic effect, fish when concentration is greater than 1mg/L in water can be dead, and is neutralized to refinery alkaline sewage When, sulfide is converted to hydrogen sulfide gas and spills into air, can constitute a threat to the life security of the mankind.Refinery alkaline sewage In phenolic substances belong to high poison substance, be prototype matter poisonous substance, to all toxic effect of all biological livings.High concentration phenols It can make protein coagulating, cause tissue damage, necrosis and poisoning, the fish in water can also be made dead;Low concentration phenols can make egg White matter denaturation, long-term drinking source water containing phenol can generate the symptoms such as headache, dizziness, insomnia, fatigue.
The biodegradability of usual waste water can use five-day BOD/COD (BOD5/ COD) ratio come It indicates, it is considered that work as BOD5/ COD is to be easy biology explanation 0.3 ~ 0.35 or more.And refinery alkaline sewage is given birth to The property changed test result shows its BOD5/ COD value is far below above-mentioned minimum, is 0.002.It is removed in high concentration refinery alkaline sewage Outside sulfide and phenolic compound containing high concentration, also contain poisonous and harmful substance, if being directly discharged to sewage plant Biological processing unit must will affect the stable operation of sewage treatment facility and the qualified discharge of waste water;Have if these are toxic Evil substance will jeopardize the ecological environment of water body with discharge of wastewater to water body, or even influence mankind's safe drinking water;It simultaneously also can be right Atmospheric environment around plant area causes odor pollution.
Therefore, the hot spot and problem for being treated as petroleum refining enterprise concern of refinery alkaline sewage.
Summary of the invention
The object of the present invention is to provide a kind of for refinery alkaline sewage high concentration, feature difficult to degrade and poisonous and harmful, Using Fenton oxidation and activated carbon adsorption as the refinery alkaline sewage processing method of technology.
The present invention adopts the following technical scheme:
A kind of processing method of refinery alkaline sewage comprising following steps:
(1) pH for adjusting refinery alkaline sewage is 2 ~ 8;
(2) Fenton oxidation: mass concentration ratio H is carried out to refinery alkaline sewage2O2/ COD=0.5 ~ 5.0, mass concentration ratio H2O2/ Fe2+=20,10 ~ 30min of reaction time;
(3) pH through step (2) treated waste water is adjusted to neutrality;
(4) waste water that step (3) obtains is centrifuged, revolution is 800 ~ 1500 r/min, 15 ~ 25min of centrifugation time;
(5) waste water through step (4) carries out activated carbon adsorption: active carbon dosage 10 ~ 50g/L, pH are 6 ~ 8, adsorption time 1 ~ 4 hours.
Wherein, in the step (1), the pH for adjusting refinery alkaline sewage is 2 ~ 6.
Wherein, in the step (1), the pH for adjusting refinery alkaline sewage is 4.5.
Wherein, in the step (2), mass concentration ratio H2O2/ COD=4.5, reaction time 15min.
Wherein, in the step (2), mass concentration ratio Fe2+/COD =0.015~0.2。
Wherein, in the step (2), mass concentration ratio Fe2+/COD =0.125。
Wherein, the centrifuge RPMs in the step (4) are 1000 r/min, centrifugation time 20min.
Wherein, in the step (5), active carbon dosage 30g/L, pH 7, adsorption time is 2 hours.
The beneficial effects of the present invention are:
For China petroleum refining enterprise high-concentration hardly-degradable oil refining wastewater (refinery alkaline sewage), Fenton oxidation-is proposed The research of activated carbon adsorption is imagined, which is different from the experimental design technique of other people and group completely, with emphasis on examination Treatment effect of the technology to refinery alkaline sewage.
Fenton oxidation technology is a kind of high-level oxidation technology, and can effectively remove toxic has with difficult to degrade in degrading waste water Harmful organic pollutant.The feature of, COD value height high for refinery alkaline sewage coloration, biodegradability difference, has carried out a system Column experiment.Research contents mainly includes Fenton oxidation, the influence rule and treatment effect that active carbon absorption technology is run, and Experimental result is analyzed and has been discussed.
Refinery alkaline sewage carries out activated carbon adsorption after Fenton reagent aoxidizes, and water outlet meets country " at town sewage First discharge standard as defined in reason factory's pollutant emission standard (GB18918-2002) ".
Technology assessment carried out to Fenton oxidation+active carbon absorption technology of proposition, at the same with refinery alkaline sewage The more technology comparison of current application, refinery alkaline sewage Fenton oxidation+active carbon absorption technology is technically feasible 's.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Fig. 2 is mass concentration ratio H2O2Influence diagram of/the COD to COD removal effect.
Fig. 3 is mass concentration ratio Fe2+Influence diagram of/the COD to COD removal effect.
Fig. 4 is influential effect figure of the solution ph to COD.
Fig. 5 is influential effect figure of the reaction time to COD.
Fig. 6 is hydrogen peroxide dosage in H2O2/Fe2+To the influence diagram for the treatment of effect when=20.
Fig. 7 is coloration variation diagram.
Fig. 8 is the variation diagram of pH value.
Fig. 9 is UV-visible absorption spectrum.
Figure 10 is infrared spectrogram.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention is described in detail below with reference to the accompanying drawings and embodiments, should Embodiment is exemplary, and for explaining only the invention, is not constituted and is limited to protection scope.
Process flow chart of the invention is as shown in Figure 1, refinery alkaline sewage needs acid adding to adjust before Fenton process oxidation PH, so that Fenton reagent plays optimal treatment effect;Waste water is directly entered Fenton oxidation processing stage after acidification, workshop section's mesh Fe after being strong oxidizing property and reaction by Fenton reagent3+Flocculation organic matter most of in refinery alkaline sewage Removal;Water outlet plus alkali neutralization after Fenton's reaction, then be centrifuged, supernatant indices after activated carbon adsorption reach Correlation water requirement.
1 orthogonal experiment of embodiment
Fenton process is by Fe2+And H2O2The Fenton reagent of composition, it passes through Fe2+It is catalyzed H in acid condition2O2Decompose generation Hydroxyl radical free radical (OH) carrys out attack organic molecule internal key, and the generation of hydroxyl radical free radical is limited by many factors, Reaction condition needed for different industrial wastewaters is not also identical, should first determine its each influence factor for actual industrial wastewater Between primary-slave relation.
The present invention devises mass concentration ratio H2O2/ COD(A), mass concentration ratio Fe2+/ COD(B), solution initial pH value (C), the reaction time (D) is the orthogonal test of 4 factor, 3 level of variable, and reaction carries out at room temperature.Orthogonal experiment because Plain water-glass is shown in such as table 1.
1 orthogonal test factor level table of table
Since most experiments are all lower to the removal rate of coloration in selected horizontal extent, to orthogonal test As a result it when for statistical analysis, is only characterized with COD removal rate.The results are shown in Table 2 for specific experiment.
2 orthogonal experiments analytical table of table
Pass through the analysis to orthogonal experiment data, it can be deduced that one draws a conclusion: in selected influence factor, mass concentration Compare H2O2/ COD influences maximum, followed by mass concentration ratio Fe on the removal of refinery alkaline sewage COD2+/ COD, followed by solution PH value, the influence in reaction time is minimum;By can be seen that its preferable processing operation condition is A in tablek3Bk3Ck2Dk2, i.e. matter Measure concentration ratio H2O2/ COD=3.5, mass concentration ratio Fe2+/ COD=0.075, solution ph 5, reaction time 30min.
2 mass concentration ratio H of embodiment2O2Influence of/the COD to treatment effect
Experiment carries out under conditions of 28.0 ± 0.5 DEG C of room temperature, and fixed other factors are constant, i.e. mass concentration ratio Fe2+/COD It is 0.075, the initial pH value of waste water is 5, reaction time 30min, investigation quality concentration ratio H2O2The variation of/COD is to Fenton oxygen Change method handles the influence rule and optimum process operating parameter of refinery alkaline sewage COD removal rate, as a result sees Fig. 2.
As seen from Figure 2, with mass concentration ratio H2O2The increase of/COD, COD removal take the lead in tending towards stability after increasing. As mass concentration ratio H2O2When/COD is 0.5, the COD removal rate of waste water is only 39.84% at this time;And mass concentration ratio H2O2/COD When increasing to 2.5, the removal rate of COD increases to 92.25%;Hereafter the removal rate of COD starts to tend towards stability, and works as mass concentration ratio H2O2COD removal rate becomes 94% when/COD is 3.5, only increases 1.75%.Accordingly, it is determined that it is dense tentatively to select optimal quality Degree compares H2O2/ COD is 2.5.
This is because in mass concentration ratio H2O2/ COD it is lower when, the hydroxyl radical free radical (OH) of generation is less, with matter Measure concentration ratio H2O2The increase of/COD adds the increase of dioxygen water in refinery alkaline sewage, promotes the progress of reaction equation (2), So that the hydroxyl radical free radical quantity generated increases, more hydroxyl radical free radical OH participate in the reaction of oxidation of organic compounds in solution, Thus the removal rate of COD is with mass concentration ratio H2O2/ COD increases and constantly increases.And mass concentration ratio H2O2/ COD continues to increase Greatly, i.e. H2O2When dosage is excessive, excessive H in system2O2Status solution, and excessive H can be produced from2O2With Fe3+Occur anti- Hydroperoxyl radical (HO should be generated2), the ability ratio OH of oxidative degradation organic matter is weak, and hydroperoxyl radical also can Water is generated with hydroxyl radical reaction, therefore COD removal rate is caused to will not continue to quickly increase.
From experimental phenomena it is observed that in mass concentration ratio H2O2When/COD is lower, bubble-free is generated in conical flask; And there are minute bubbles to emerge when ratio increases, in waste water, this is because being had occurred between hydroxyl radical free radical from annihilation reaction, reduce The utilization rate of hydroxyl radical free radical, so that COD removal rate becomes smaller;In addition, H remaining in waste water after oxidation reaction2O2Also can Potassium bichromate reaction in COD testing tube, causes the test value of COD higher, reduces the removal rate of COD to a certain extent. Therefore, it requires to heat waste water after the completion of reaction, further to remove remaining H2O2
3 mass concentration ratio Fe of embodiment2+Influence of/the COD to treatment effect
Different quality concentration ratio Fe is investigated2+Influence of/the COD to COD removal rate in Fenton oxidation method processing refinery alkaline sewage The determination of action rule and optimal procedure parameters, is as a result shown in Fig. 3.Experiment is at 28.0 ± 0.5 DEG C of room temperature, the mass concentration of hydrogen peroxide Than for H2O2/ COD=2.5, the initial pH value of waste water are 5, and the reaction time is to carry out under conditions of 30 minutes.
As seen from Figure 3, with mass concentration ratio Fe2+The increase of/COD, the COD removal of waste water take the lead in subtracting after increasing It is small.As mass concentration ratio Fe2+When/COD increases to 0.125 by 0.015, wastewater COD removal rate is gradually increased, and is increased by 74.85% To 94%;And work as mass concentration ratio Fe2+When/COD continues to increase to 0.2, COD removal rate is reduced to 90.17% instead.
This is because in Fenton reagent oxidation system, as mass concentration ratio Fe2+When/COD is lower, the hydroxyl free of generation Base OH is less, and limitation has carried out the progress of oxidation reaction, and most organic matter cannot be degraded in waste water, thus COD is removed Rate is relatively low;As mass concentration ratio Fe2+When/COD constantly increases, i.e. Fe2+Dosage increases, so that the hydroxyl radical free radical generated Quantity is also increasing, and COD removal rate is also continuously increased, as mass concentration ratio Fe2+COD removal rate reaches when/COD is 0.125 Maximum value 94%;And as mass concentration ratio Fe in system2+When/COD is greater than 0.125, Fe2+Promote H2O2Decomposition accelerate instead The progress answered, but great amount of hydroxy group free radical OH assembles and reacts to each other and generates water and O at the same time2, reduce H2O2It utilizes Rate.In terms of experimental data, mass concentration ratio Fe2+It is optimum response point that/COD, which is 0.125,.
Influence of 4 initial pH value of embodiment to treatment effect
Initial pH on wastewater value generates large effect to Fenton reagent oxidation reaction, and pH value is too high or too low to be all unfavorable for hydroxyl certainly By the generation of base.A large amount of experimental study report, the optimal pH value range of Fenton reagent oxidation reaction are 3 ~ 5, the range and useless The type relationship of Organic substance in water is little.
At 28.0 ± 0.5 DEG C of room temperature, mass concentration ratio H2O2/ COD is 2.5, mass concentration ratio Fe2+/ COD is 0.075, instead Between seasonable under conditions of 30 minutes, waste water difference initial pH value has been investigated to COD in Fenton oxidation method processing refinery alkaline sewage The influence of removal rate, is as a result shown in Fig. 4.
As seen from Figure 4, with the increase of initial pH on wastewater value, COD removal takes the lead in reducing again after increasing.At the beginning of waste water When beginning pH value is 2, COD removal rate is 92.25%;When initial pH value increases to 3, the removal rate of COD reaches maximum value and is 94.15%;Hereafter continue to increase initial pH on wastewater value, wastewater COD removal rate is begun to decline instead.Therefore, preferable waste water is initial PH value range is 3.
This is because, the initial pH value variation of waste water has directly influenced Fe2+And Fe3+Equilibrium relation, and then influence Fenton reagent generates the ability of hydroxyl radical free radical, therefore initial pH on wastewater value is too high or too low, all unfavorable to the removal of COD. When initial pH on wastewater value is excessively high, Fe3+It is easy to generate Fe (OH)3Precipitating inhibits Fe3+Generation so that generating hydroxyl radical free radical Quantity reduces, and the COD removal rate of waste water is caused to have a degree of decline;Conversely, pH value can inhibit Fe when too low3+Generation, Influence catalysis reaction.Therefore, it is 3 that optimal initial pH value is selected in this experiment.
Influence of 5 time of embodiment to treatment effect
In the case where fixed reaction rate, the reaction time directly affects the degree that reaction carries out.Therefore, if the reaction time compared with It is short, it will cause reaction and be not thorough, expected processing requirement cannot be reached;If the time of opposite reaction is very long, not only can It wastes time, while will increase the volume of reactor in actual production, cause unnecessary waste.
Experiment is at 28.0 ± 0.5 DEG C of room temperature, mass concentration ratio H2O2/ COD is 2.5, mass concentration ratio Fe2+/ COD is 0.125, initial pH on wastewater value carries out under conditions of being 3, has investigated the differential responses time to Fenton oxidation method processing refinery alkaline residue The influence that COD is removed in waste water, is as a result shown in Fig. 5.
As seen from Figure 5, the speed of Fenton's reaction quickly, reacts preceding 5 minutes COD removal rates and has just reached 50% or more, This illustrates that the reaction rate of Fenton oxidation is very fast;When reaction time has 5 minutes to 15 minutes, the COD removal rate of waste water is at any time Between extension and be continuously increased, this shows that reaction rate is stablized, and the organic matter in waste water, which is constantly oxidized, to be decomposed.When reaction is super After spending 30 minutes, COD removal rate remains unchanged substantially.
This is because in the reaction incipient stage, ferrous ion Fe2+Catalysis generates a large amount of hydroxyl radical free radical, hydroxyl free Oxidation reaction quickly occurs for the organic matter in base and waste water, by figure it can also be seen that reaction 5 minutes to 15 minutes, oxidation speed Rate is fast;After the time being more than 15 minutes, the rate that catalysis generates hydroxyl radical free radical declines to a great extent, therefore the COD removal rate of waste water Also start to tend to mitigate.
In summary it analyzes, the optimum reacting time for choosing Fenton oxidation degradation refinery alkaline sewage is 15 minutes.
6 mass concentration ratio H of embodiment2O2/Fe2+Influence to treatment effect
Mass concentration ratio H2O2/ COD and Fe2+/ COD has important influence to the generation of Fenton reagent hydroxyl radical free radical.But In H2O2And Fe2+Between reciprocation (i.e. H2O2And Fe2+Ratio) Fenton reagent can also be had an impact.Therefore, in Fenton The reagent of reagent answers strict control H in the application2O2And Fe2+Ratio.It proves after study, organic matter of the ratio with processing Type is related, the optimal H of variety classes waste water2O2And Fe2+Ratio it is different.
By experimental data, it can be concluded that, Fenton process handles the optimal H of oil refining wastewater2O2/Fe2+=20:1。
At 28.0 ± 0.5 DEG C of room temperature, fixed mass concentration ratio H2O2/Fe2+For 20:1, initial pH on wastewater value is 3, when reaction Between to have investigated different quality concentration ratio H under conditions of 15 minutes2O2Influence of/the COD to COD removal rate, is as a result shown in Fig. 6.
As seen from Figure 6 in fixed mass concentration ratio H2O2/Fe2+Under the conditions of 20:1, with H2O2/ COD mass concentration The increase of ratio, wastewater COD removal rate first increases to tend towards stability afterwards, the further raising but it is got back.Work as mass concentration ratio H2O2When/COD is 4.5, it is 98.63% that the COD removal rate of waste water, which reaches maximum value, and COD value of waste water is 252mg/ after aoxidizing at this time L.Accordingly, it is determined that H2O2The optimal mass concentration ratio of/COD is 4.5.
Comparative example blank assay
In the case where testing obtained optimal processing parameter above, i.e. mass concentration ratio H2O2/Fe2+For 20:1, mass concentration ratio H2O2/ COD is 4.5, and initial pH on wastewater value is 3, and the reaction time is 15 minutes, as a comparison with distilled water, according to the above identical step Blank assay is done, influence of the addition to measurement result of Fenton reagent, distilled water and refinery alkaline sewage experimental result pair are investigated Such as table 10.
Seen from table 3, the average COD value of blank assay is 5.0 ~ 6.0mg/L, and higher than the COD value of pure water, reason may It is micro Fe remaining in treatment fluid2+And H2O2, and the experimental principle for measuring COD is redox reaction, all has reproducibility, The COD value of waste water is increased to a certain extent.
3 blank assay data of table
Effect example 1
Refinery alkaline sewage is investigated under following experiment conditions, i.e. 28.0 ± 0.5 DEG C of room temperature, mass concentration ratio H2O2/Fe2+For 20:1, mass concentration ratio H2O2/ COD is 4.5, and initial pH on wastewater value is 3, and the reaction time is oxidation front and back under conditions of 15 minutes The variation of solution coloration changes with time situation.
Fenton oxidation method handles refinery alkaline sewage, and the chroma in waste water variation of oxidation front and back is as shown in Figure 7.
As seen from Figure 7, dark-brown of the refinery alkaline sewage from before aoxidizing become oxidation after color it is transparent, coloration by 2000 times before oxidation are reduced to 0 ~ 1 times, and chroma removal rate reaches national town sewage first discharge standard close to 100%.
Effect example 2
Refinery alkaline sewage is investigated under following experiment conditions, i.e. 28.0 ± 0.5 DEG C of room temperature, mass concentration ratio H2O2/Fe2+For 20:1, mass concentration ratio H2O2/ COD is 4.5, and initial pH on wastewater value is 3, and the reaction time is oxidation front and back under conditions of 15 minutes Solution ph changes with time situation.
During Fenton oxidation method handles refinery alkaline sewage, wastewater pH changes with time such as Fig. 8.
As seen from Figure 8, it reacts the initial stage, oxidation of organic compounds generates a large amount of H to Fenton reagent in acid condition+, this reduces the pH value of waste water quickly, and the pH value of waste water is reduced to 1.23 by 3 in reaction 15 minutes.This is because refinery The CO of the organic matter degradation carboxylic acid generated and dissolution in alkaline sewage2The pH value of system is caused to decline.But with reaction The reduction and exothermic heat of reaction for carrying out useless Organic substance in water make the CO being dissolved in water2It releases, leads to returning for pH value of waste water It rises.
The 3 biodegradability comparative analysis of effect example
The biodegradable of waste water, i.e., it is that one of waste water is important that useless Organic substance in water was degraded by microorganisms, which is difficult to degree, Index.The evaluation method of biodegradability is BOD5/ COD value, as the BOD of waste water5Think that waste water is not easy to give birth to when/COD value is less than 0.25 Object degradation;And think that waste water is easily biodegradable when the value is greater than 0.45.According to testing the optimum test condition obtained above Under, the biochemical oxygen demand (BOD) and biodegradability for measuring waste water are shown in Table 4 compared with the waste water before processing.
The variation table of 4 biochemical oxygen demand (BOD) of table and biodegradability
As shown in Table 4, refinery alkaline sewage is after Fenton reagent aoxidizes, BOD5/ COD is improved everywhere from pervious 0.002 0.4 ~ 0.5 after reason, the biodegradability of waste water greatly improves, and is conducive to going on smoothly for subsequent biochemical processing.
4 ultraviolet-visible light spectrum analysis of effect example
Due to containing a large amount of phenolic compound, thiophene, thiophenol etc. in refinery alkaline sewage, contain conjugated double bond in these substances With the characteristic groups such as phenyl ring, there are many " p " or " π " bonding electron transition compared with low energy in these functional groups, lead to refinery Organic matter in alkaline sewage has obvious absorption in ultra-violet (UV) band and visual field.
Uv-visible absorption spectra scanning has been carried out with the refinery alkaline sewage of differential responses time 0,5,10,15min, Using spectrophotometry.Water sample is fitted into 1cm glass cuvette, using distilled water as reference liquid, with UV762 UV, visible light point Light photometer all band in 200 ~ 400nm of near ultraviolet band scans, and it is as shown in Figure 9 to obtain ultraviolet-visible spectrum.
It can be seen in figure 9 that untreated refinery alkaline sewage has characteristic absorption peak at 270nm, absorbance is 0.158.Since the major pollutant of alkaline sewage is the macromolecular complex such as aphthenic acids, creosote, thiophenol, thiophene phenol, mercaptan, thioether Matter contains benzene ring structure in phenolic compounds, can have characteristic absorption between 200 ~ 400nm.Therefore it may be speculated that alkaline sewage exists Absorption peak at 270nm is mainly by the creosote containing benzene ring structure, thiophenol, the contribution of thiophene phenol.
With the continuity in reaction time, apparent downward trend is presented in the absorption peak at 270nm, until the reaction time 15 minutes When absorption peak of the refinery alkaline sewage in ultraviolet-ray visible absorbing light area all disappear, illustrate the organic constitution hair in waste water Significant changes are given birth to, while not new absorption peak in ultraviolet visible light region occurs.It can be considered that Fenton process is certain The structure that phenyl ring can be destroyed in degree, improves the biodegradability of waste water.
The analysis of 5 Fourier infrared spectrum of effect example
The pretreatment of infrared spectroscopy sample: taking refinery alkaline sewage and oxidation to be discharged each 300mL, water sample pH value be adjusted to 6 ~ 8, with Terminate Fenton's reaction;Then it places and is concentrated and dried in rotary evaporator.As for thermostatic drying chamber when water sample residue about 10 ~ 15mL Interior drying to powder fills, and collects powder after group, and standby Fourier infrared spectrum tests and analyzes measurement and uses.
In order to further appreciate that the mechanism of Fenton oxidation degradation refinery alkaline sewage, test to the concentration before and after wastewater oxidation Solid powder has carried out FITR IR spectrum scanning, and gained infrared spectrogram is as shown in Figure 10.
In 2500 ~ 4000cm of wave-length coverage-1For on-the C-H and unsaturated atom on X-H(-O-H, saturation atom=C- H stretching vibration area), and in nonpolar solvent, association occurs when concentration is larger, peak shape is wider.It can be with by Figure 10 Find out have apparent absorption between wave-length coverage 2500 ~ 3600 in figure 1, illustrate mercaptan, sulphur in refinery alkaline sewage The absorption peak for the dimer that association is formed occurs for the m- OH of the molecules such as ether, phenol and aphthenic acids ,-CH and=C-H;And it is dropped in Fenton oxidation This wave band absorbs obvious weaken after solution, it was demonstrated that these characteristic groups are degraded in oxidation process.
In 1900 ~ 1200 cm of wave-length coverage-1For double bond stretching vibration area, such as C=C and C=O.There are four inhale by C=C of phenyl ring Receive 1600,1585,1500,1450 cm of peak-1, it is the important symbol identified whether there is or not phenyl ring, as seen from Figure 10 1600 after oxidative degradation ~1400 cm-1, place absorbs wave crest and significantly reduces, becomes simple, absorbance is substantially reduced, and illustrates that phenyl ring is obviously oxidized degradation.This Outside, after oxidation in figure 1639 cm of 2(wavelength-1) at there is characteristic absorption peak, illustrate aphthenic acids in refinery alkaline sewage, phenol, The organic matters such as mercaptan and thioether are oxidized the substances such as the carboxylic acid for resolving into small molecule.
In conclusion the present invention carries out treatment process of the Fenton reaction system to refinery alkaline sewage by experiment Research.The optimum operation condition of test has been determined using orthogonal test, and to influence factor therein such as hydrogen peroxide dosage, Ferrous ion dosage, solution initial pH value, reaction time, dosing method of hydrogen peroxide etc. are studied, them are analyzed Influence situation to treatment process, obtains by experiment as drawn a conclusion:
1) the Fenton process processing main influence factor of refinery alkaline sewage has mass concentration ratio H2O2/ COD, mass concentration ratio Fe2+/ COD, initial pH value and reaction time, the primary-slave relation for obtaining each influence factor by orthogonal test is: H2O2/ COD mass concentration The removal for comparing refinery alkaline sewage COD influences maximum, followed by Fe2+Throwing/COD mass concentration ratio, followed by the pH value of solution, The influence in reaction time is minimum.
2) optimal processing parameter of Fenton process processing refinery alkaline sewage is mass concentration ratio H2O2/ COD=4.5, quality are dense Degree compares H2O2/Fe2+=20, solution initial pH value be 3, the reaction time be 15 minutes, at this time wastewater effluent COD value be 250 ~ 300mg/L, COD removal rate are 99% or so, and chroma removal rate is almost 100%.
3) under the conditions of optimal technological parameter, wastewater effluent BOD5/ COD value is increased to oxidation by 0.002 before aoxidizing Afterwards 0.4 ~ 0.5, the biodegradability of waste water is greatly improved, and provides preferable condition for the subsequent biochemical treatment of waste water.
4) activated carbon adsorption
The direct Fenton oxidation processing of refinery alkaline sewage is not met by the requirement of standard discharge, needs to take it further Treatment measures, and activated carbon adsorption can remove the organic matter in water removal, therefore propose at Fenton oxidation-activated carbon adsorption joint Science and engineering skill.
Refinery alkaline sewage is after Fenton reagent aoxidizes, by the preferred 1000r/min of 800 ~ 1500r/min() centrifugation After 20min, activated carbon adsorption is carried out, the suitable process Parameter Conditions of absorption are: active carbon dosage 30g/L, solution ph 6 ~ 8, adsorption time is 2 hours, and under conditions of optimal, water outlet meets national " urban wastewater treatment firm pollutant emission standard (GB18918-2002) " first discharge standard as defined in.
5) it can be seen that Fenton reagent from ultraviolet-visible absorption spectroscopy figure and Fourier infrared spectrum figure for refinery alkaline residue Characteristic contamination matter such as aphthenic acids, phenol and alcohol ether etc. in waste water, oxidative degradation remove or are oxidized to the carboxylic acid of small molecule.
Embodiment described above only describe the preferred embodiments of the invention, and but it is not limited to this, this The technical staff in field is easy to understand spirit of the invention according to above-described embodiment, and makes different amplification and variation, but As long as it does not depart from the spirit of the invention, all within protection scope of the present invention.

Claims (8)

1. a kind of processing method of refinery alkaline sewage, which is characterized in that it includes the following steps:
(1) pH for adjusting refinery alkaline sewage is 2 ~ 8;
(2) Fenton oxidation: mass concentration ratio H is carried out to refinery alkaline sewage2O2/ COD=0.5 ~ 5.0, mass concentration ratio H2O2/Fe2 +=20,10 ~ 30min of reaction time;
(3) pH through step (2) treated waste water is adjusted to neutrality;
(4) waste water that step (3) obtains is centrifuged, revolution is 800 ~ 1500 r/min, 15 ~ 25min of time;
(5) waste water through step (4) carries out activated carbon adsorption: active carbon dosage 10 ~ 50g/L, pH are 6 ~ 8, adsorption time 1 ~ 4 hours.
2. the processing method of refinery alkaline sewage according to claim 1, which is characterized in that in the step (1), adjust The pH of refinery alkaline sewage is 2 ~ 6.
3. the processing method of refinery alkaline sewage according to claim 2, which is characterized in that in the step (1), adjust The pH of refinery alkaline sewage is 4.5.
4. the processing method of refinery alkaline sewage according to claim 1, which is characterized in that in the step (2), quality Concentration ratio H2O2/ COD=4.5, reaction time 15min.
5. the processing method of refinery alkaline sewage according to claim 1, which is characterized in that in the step (2), quality Concentration ratio Fe2+/COD =0.015~0.2。
6. the processing method of refinery alkaline sewage according to claim 5, which is characterized in that in the step (2), quality Concentration ratio Fe2+/COD =0.125。
7. the processing method of refinery alkaline sewage according to claim 1, which is characterized in that in the step (4) from Heart revolution is 1000 r/min, time 20min.
8. the processing method of refinery alkaline sewage according to claim 1, which is characterized in that in the step (5), activity Charcoal dosage 30g/L, pH 7, adsorption time are 2 hours.
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