CN108147614A - A kind of preprocess method and device for refining oil reverse osmosis concentrated water - Google Patents

A kind of preprocess method and device for refining oil reverse osmosis concentrated water Download PDF

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Publication number
CN108147614A
CN108147614A CN201611103366.7A CN201611103366A CN108147614A CN 108147614 A CN108147614 A CN 108147614A CN 201611103366 A CN201611103366 A CN 201611103366A CN 108147614 A CN108147614 A CN 108147614A
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China
Prior art keywords
activated carbon
concentrated water
catalyst
water
reverse osmosis
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CN201611103366.7A
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Chinese (zh)
Inventor
王雪清
郝晓霞
蒋广安
马传军
郭宏山
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Priority to CN201611103366.7A priority Critical patent/CN108147614A/en
Publication of CN108147614A publication Critical patent/CN108147614A/en
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature 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
    • C02F2103/365—Nature 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)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage

Abstract

The present invention relates to it is a kind of refine oil reverse osmosis concentrated water preprocess method, including（1）Filtration treatment：The pH value for adjusting reverse osmosis concentrated water is 9 13, filter and remove suspended substances；（2）Catalytic ozonation：Concentrated water carries out catalytic ozonation processing after filtering, the catalyst includes nucleocapsid component, the nucleocapsid component is using activated carbon as core, using the amorphous silica-alumina containing transition metal and rare earth metal as shell, on the basis of the weight of activated carbon and amorphous silica-alumina, activated carbon accounts for 10% 70%, and amorphous silica-alumina accounts for 30% 90%；（3）Stablize processing：Oxidation water outlet enters stabilization pond, decomposes residual ozone in water, enters back into biological treatment system.The present invention is by adjusting the water quality of reverse osmosis concentrated water and with reference to special catalyst, can improve ozone utilization rate, effectively remove the COD difficult to degrade in concentrated water, improve its biodegradability, processed waste water can directly carry out biochemical treatment.

Description

A kind of preprocess method and device for refining oil reverse osmosis concentrated water
Technical field
The invention belongs to refinery(waste) water process fields, and in particular to reverse osmosis caused by during a kind of refinery(waste) water reuse The preprocess method and device of saturating concentrated water.
Background technology
Increasingly stringent with national environmental protection management, the qualified discharge pressure that oil refining enterprise faces is increasing.On the one hand Pollutant emission standard is gradually tightened, COD in externally discharged waste water（COD）Discharge standard is reduced to 60mg/L, component environment Sensitive area is even lower.On the other hand to save water resource, encouragement enterprise implement reusing sewage reduces fresh water consumption, by Externally discharged waste water amount caused by this is reduced and pollutant concentration improves, and further increases the difficulty of qualified discharge.Oil refining enterprise is dirty The reverse osmosis concentrated water generated during water reuse is a kind of high concentration, used water difficult to degradate, and the pollutants such as COD are concentrated 3- in concentrated water 4 times, generally in 100-200mg/L.This burst of concentrated water is directly returned to sewage farm by Some Enterprises at present, due to pollutant concentration High and biodegradability is poor, influences the up to standard of final externally discharged waste water, it is therefore desirable to individually be pre-processed.
Catalytic ozonation is one of hot spot direction of current water technology research, uses it for reverse osmosis concentrated water process Report also have very much.CN102040312A discloses a kind of processing method of reverse osmosis concentrated water, using " laminated filter+more The process flow of phase O3 catalytic oxidation reaction+ozone layer destroying tower+biochemical reaction tank ", wherein catalyst are zirconia titanate, biochemical anti- Ying Chizhong needs to add special bacteria and Powdered Activated Carbon.CN102372376A discloses a kind of processing method of reverse osmosis concentrated water, Using the process flow of " heterogeneous catalytic ozonation+powder electroless plating+ultrafiltration ", used catalyst is high-temperature metal ion Loaded catalyst.CN102070238A discloses a kind of technique side of catalytic ozonation processing oil refining wastewater reverse osmosis concentrated water Method, using the process flow of " ozone pre-oxidation+catalytic ozonation ", used catalyst is prepared based on aluminium oxide.More than work Skill is on the basis of catalytic ozonation or increases activated carbon adsorption or adds special bacteria or increase leading portion pre-oxidation etc., a side Face causes technological process longer, increases investment and operating cost, on the other hand also reflects that catalyst performance is limited, individually uses The effect of catalytic ozonation+routine biochemistry processing can not meet emission request.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preprocess method and device for refining oil reverse osmosis concentrated water.It should Method is by adjusting the water quality of reverse osmosis concentrated water and with reference to special catalyst, can improve ozone utilization rate, effectively remove concentrated water In COD difficult to degrade, improve its biodegradability, processed waste water can directly carry out biochemical treatment.
The preprocess method of present invention oil refining reverse osmosis concentrated water, including following content：
（1）Filtration treatment：The pH value for adjusting reverse osmosis concentrated water is 9-13, and filtering removes the suspended matter in reverse osmosis concentrated water；
（2）Catalytic ozonation：Concentrated water carries out catalytic ozonation processing after filtering, and the catalyst includes nucleocapsid group Point, which is using activated carbon as core, using the amorphous silica-alumina containing transition metal and rare earth metal as shell, with activity On the basis of the weight of charcoal and amorphous silica-alumina, activated carbon accounts for 10%-70%, and amorphous silica-alumina accounts for 30%-90%；
（3）Stablize processing：Oxidation water outlet enters stabilization pond, decomposes residual ozone in water, enters back into biological treatment system.
In the present invention, the pH value of reverse osmosis concentrated water is adjusted to 9-13, preferably 10-11, hydroxide can be reduced in this way The yield of precipitation is not softening raw water.
In catalyst of the present invention, the base metal in the transition metal the 4th and 5 periods in the periodic table of elements, such as It can be selected from one or more in vanadium, chromium, manganese, iron, cobalt, copper and titanium.The rare earth metal is lanthanum, one kind in cerium or more Kind.The granularity of the activated carbon is -300 mesh of 150 mesh.
In catalyst of the present invention, using transition metal and rare earth metal as active metal component, using the weight of catalyst as base Standard, the content of transition metal oxide is 1%-15%, and preferably 1%-10%, the content of rare-earth oxide is 1%-15%, excellent It is selected as 1%-10%, the content of activated carbon and amorphous silica-alumina is 70%-98%, preferably 80%-98%.
In amorphous silica-alumina of the present invention containing transition metal and rare earth metal, using the weight of amorphous silica-alumina as base Standard, the content of silica is 10%-90%, preferably 30%-70%.
Auxiliary agent can be contained in amorphous silica-alumina of the present invention containing transition metal and rare earth metal, the auxiliary agent can Think the common adjuvant component of carrier, for example, in titanium, zirconium, magnesium, zinc etc. it is one or more, weight content based on the element is 10% Hereinafter, preferably 1%-5%.
The preparation process of catalyst of the present invention, including following content：（1）- 300 mesh activated carbon of 150 mesh is beaten； （2）Step is introduced during amorphous silica-alumina and the plastic of transition metal and rare-earth metal complex are prepared using coprecipitation （1）Obtained activated carbon slurries；（3）Step（2）Material after obtained plastic carries out aging, is filtered, washed, dries；（4） By step（3）Catalyst is made in the material of gained.Preferably at least using one of following methods：
A, by step（3）The material of gained roasts under inert gas shielding, obtains catalyst；
B, by step（3）The material forming of gained after drying, roasts under inert gas shielding, obtains catalyst；
C, by step（3）The material of gained roasts under inert gas shielding, then again through molding, after dry, in inert gas Protection is lower to be roasted, and obtains catalyst.
In the preparation method of catalyst of the present invention, step（1）Conventional Powdered Activated Carbon commodity can be selected in the activated carbon, Such as all kinds of wood activated charcoals, active fruit shell carbon, active carbon from coal.Activated carbon used in the present invention is powdered active carbon, Granularity 150-300 mesh, specific surface area 500-3000m2/ g, hole hold 0.5-1.8cm3/ g, average pore radius 1-10nm.
In the preparation method of catalyst of the present invention, step（1）The activated carbon mashing is carried out using conventional method, generally Using add in water, low-carbon alcohols it is one or more be beaten, wherein low-carbon alcohols are one in the monohydric alcohol that carbon atom number is 1-5 Kind is a variety of.
In the preparation method of catalyst of the present invention, step（1）It is preferred that activated carbon is first handled using carbohydrate, then beaten Slurry.The carbohydrate is one or more of monosaccharide and disaccharide, polysaccharide, and preferably carbon atom number is the carbohydrate of 3-20, such as： It is one or more in triose, tetrose, pentose, hexose, maltose, glucose, sucrose, one preferably in glucose, sucrose Kind is a variety of.The carbohydrate dosage accounts for the 2%-50% of activated carbon weight, preferably 5%-20%.Carbohydrate processing activated carbon can incite somebody to action Carbohydrate is directly mixed with activated carbon, and carbohydrate can also be dissolved in solvent and adds activated carbon, and solvent therein is water, low-carbon alcohols （I.e. carbon atom number is the monohydric alcohol of 1-5）In it is one or more.Carbohydrate handle activated carbon when, liquid consolidate volume ratio 10 with Under, preferably in 1-5.After carbohydrate processing activated carbon, excessive liquid phase is preferably filtered to remove, and is then beaten again.Mashing can adopt Carried out with conventional method, it is general using plus water, low-carbon alcohols in it is one or more be beaten, wherein low-carbon alcohols are carbon atom number It is one or more in 1 ~ 5 monohydric alcohol.
In the preparation method of catalyst of the present invention, step（2）Amorphous silica-alumina and transition metal are prepared using coprecipitation It can be carried out with rare earth metal composite oxide by process well known to those skilled in the art.Usually acid material and basic species The neutralization plastic process of material.The mode of the continuous acid-base titration of soda acid may be used in plastic process, can also use two kinds of materials simultaneously Flow the mode neutralized.
In the preparation method of catalyst of the present invention, step（2）Aluminium oxide and transition metal and dilute are prepared using coprecipitation Earth metal composite oxides are in silicon source, transition metal source and rare earth metal source（Transition metal source is preferably vanadium source, chromium source, manganese One or more in source, source of iron, cobalt source, copper source and titanium source, rare earth metal source is one or more in lanthanum source, cerium source） It is reacted with precipitating reagent and carries out plastic, silicon source is aluminium chloride, one or more, used precipitating reagents one in aluminum sulfate, aluminum nitrate As be one or several kinds in sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide etc..Transition gold used in it Category source and rare earth metal source generally use soluble metallic salt（Such as nitrate, chloride etc.）, can be according to metal salt used The acid-base property of solution is mixed for being co-precipitated, can also first add in plastic cans, then with corresponding acid material or alkaline material Acid material carries out plastic with alkaline material, and more than content those skilled in the art are according to known to coprecipitation.
In the preparation method of catalyst of the present invention, step（2）It is middle that amorphous silica-alumina and transition gold are prepared using coprecipitation Belong to and rare earth metal composite oxide is silicon source, silicon source, transition metal source and rare earth metal source（Transition metal source is preferably vanadium It is one or more in source, chromium source, manganese source, source of iron, cobalt source, copper source and titanium source, rare earth metal source in lanthanum source, cerium source one Kind is a variety of）It is reacted with precipitating reagent and carries out plastic.Plastic material generally comprises silicon source（Al2(SO4)3、AlCl3、Al(NO3)3With NaAlO2One or more of Deng）, silicon source（One or more of waterglass, Ludox and organic silicon-containing compound etc.）、 Precipitating reagent（NaOH、NH4OH or CO2Deng）, used according to the different selections of plastic process, conventional mode of operation mainly has：（1） Acid aluminium salt（Al2(SO4)3、AlCl3、Al(NO3)3）With basic aluminium salt（NaAlO2）Or alkaline precipitating agent（NaOH、NH4OH）It neutralizes Plastic,（2）Basic aluminium salt（NaAlO2）With acidic precipitation agent（CO2）Neutralize plastic.Silicon source generally introduces plastic during plastic Tank, can also with neutralizing plastic again after silicon source or precipitant mix, as waterglass add in basic aluminium salt or alkaline precipitating agent into Row neutralizes plastic, and Ludox, which is added in acid aluminium salt, to carry out neutralizing plastic etc..Silicon source can also be added in after silicon source precipitates in material. It can also be by two or more combined use of aforesaid way.Transition metal source used in it and rare earth metal source are generally adopted Use soluble metallic salt（Such as nitrate, chloride etc.）, can be according to the acid-base property of metal salt solution used, with corresponding acid Property material or alkaline material be mixed for being co-precipitated, can also first add in plastic cans, then acid material is carried out with alkaline material Plastic, the above content is those skilled in the art according to known to coprecipitation.
In the preparation method of catalyst of the present invention, the coprecipitation, plastic process generally at -85 DEG C of room temperature into Row, is relatively suitably for 40-80 DEG C, preferably 50-70 DEG C.The plastic process generally carries out under certain pH value condition, allusion quotation The pH of type is 6.0-10.0, is relatively suitably for 7.0-9.5, preferably 7.5-9.0.Step（3）The aging, condition are as follows：pH For 6.0-10.0, preferably 7.0-9.5, ageing time 0.25-8 hours is relatively suitble at 0.5-5 hours, preferably 1-3 hours, Aging temperature be -85 DEG C of room temperature, preferably 40-80 DEG C.Temperature and pH and temperature during neutralization and pH during aging is preferably identical.
In the preparation method of catalyst of the present invention, step（3）The mode of washing of the material can select mashing washing, mistake Add the modes such as water washing, lower alcohols washing during filter, the temperature of washing should be within the temperature range of -90 DEG C of room temperature, preferably 50- 70℃.The washing of the material generally carries out in the range of pH is 1.0-9.0, and preferably pH is 4.0-8.5.
In the preparation method of catalyst of the present invention, step（3）After washing, filtering, filter cake is dried the material, Natural drying, oven drying, spray drying, microwave drying or infra-red drying may be used in drying mode, and what is generally used is dry Dry condition is as follows：It is 1-15 hours dry at 50-150 DEG C.
In the preparation method of catalyst of the present invention, step（4）Middle method A is to obtain powdered urge without molding roasting direct Agent.Roasting condition described in method A is as follows：Calcination temperature is 450-700 DEG C, and roasting time is 1-10 hours.Method B and Molding described in method C can carry out as needed, generally strip, cylindric, spherical, irregular strip, special-shaped ball etc., and granularity can To determine as needed, generally 0.5-8.0mm.In the forming process, shaping assistant can be added in as needed as glued It is one or more in mixture, peptization acid, extrusion aid etc..Drying condition described in method B is generally at 80-200 DEG C, dry 1- 15 hours, calcination temperature was generally 450-700 DEG C, and roasting time is generally 1-10 hours.In method C, by step（3）Gained Material roasts under inert gas shielding, and selected inert gas is generally nitrogen or argon gas.The roasting condition is as follows： Calcination temperature is 450-700 DEG C, and roasting time is 1-10 hours.Then it after dry, is roasted under inert gas shielding through molding again It burns, obtains catalyst, drying condition after molding is as follows：At 80-200 DEG C, 1-15 hours dry, roasting condition is as follows：Roasting Temperature is generally 450-700 DEG C, and roasting time is generally 1-10 hours.
In the method for the present invention, one-part form fixed bed catalytic oxidation reactor can be used in catalytic ozonation processing.Ozone by Ozone generator provides, and using oxygen or air as air source, ozone concentration is generally in 1-150g/m3, preferably 40-120g/m3；Ozone Dosage is based on raw water COD concentration, generally in 30-300mg/L concentrated waters, preferably 50-250mg/L；Control catalytic ozonation anti- It is 0.1-5/h, preferably 0.5-2/h to answer air speed.
In the method for the present invention, concentrated water enters stabilization pond processing after catalytic ozonation, and the control stabilization pond residence time is 15- 60min, preferably 20-40min.Can be directly entered after stabilization sewage farm carry out biochemical treatment, control pH 6-8 it Between.Because its biodegradability be improved significantly, it can be ensured that meet emission request after processing.
The present invention for refining oil the pretreatment unit of reverse osmosis concentrated water, including filter, catalytic ozonation reactor and Stabilization pond, wherein filter are used to remove the suspended matter in reverse osmosis concentrated water；Concentrated water enters catalytic ozonation reaction after filtering It is handled in device, the catalyst of following nucleocapsid components is filled in catalytic ozonation reactor, which is Using activated carbon as core, using the amorphous silica-alumina containing transition metal and rare earth metal as shell, with activated carbon and the weight of amorphous silica-alumina On the basis of amount, activated carbon accounts for 10%-70%, and amorphous silica-alumina accounts for 30%-90%；Water outlet enters stabilization pond after ozone Oxidation Treatment, makes Remaining ozone decomposed, enters back into biological treatment system in water.
Compared with prior art, the invention has the advantages that：
（1）The catalyst prepared using specific composition and ad hoc approach can make ozone be rapidly decomposed into oxidisability stronger certainly By base, accelerate COD degradation reaction rate, improve COD removal rates, while improve the biodegradability of water outlet.In the catalyst action Under, ozone utilization rate is significantly increased, and generally can reach more than 85%, so as to reduce ozone dosage.
（2）By adjusting reverse osmosis concentrated water pH and with reference to special catalyst, catalytic ozonation effect can be improved, reduced Ozone usage amount.
（3）By filtration treatment-catalytic ozonation-stabilization processing, at existing sewage farm routine biochemistry After reason, water outlet COD can be made to be less than 60mg/L, meet emission request.
（4）The special nucleocapsid of catalyst makes it have good machinery when for refining oil reverse osmosis concentrated water process by force Degree and attrition resistance energy, and active metal not easily runs off；The stability of catalyst is good, and service life is long, it is ensured that ozone is urged Change the long-period stable operation of oxidation technology.
Description of the drawings
Fig. 1 is a kind of process flow chart for refining oil reverse osmosis concentrated water pretreatment process of the present invention.
Wherein, 1- filters, 2- catalytic ozonation reactors, 3- stabilizers, 4- lye, 5- ozone, 6- biochemical treatments Pond.
Specific embodiment
The preprocess method and device further illustrated the present invention with reference to specific embodiment, but the model of the present invention Enclose the range for being not limited solely to these embodiments.
COD in the present invention is used《The measure dichromate titration of water chemical oxygen demand》（GB 11914-89）Method It measures, BOD is used《Water quality five-day BOD（BOD5）Measure dilution and inocalation method》（HJ 505-2009）Method is surveyed It is fixed.
The present invention prepares commercially available powdery coconut husk charcoal specific surface area 928m used in catalyst2/ g, hole hold 1.0cm3/ g, average hole Radius 1.1nm, iodine sorption value 700mg/g, 200 mesh of granularity.
Solid aluminum sulfate, cerous nitrate, ferric nitrate are added in distilled water, while heats and stirs to dissolving, is obtained molten Liquid (a).Solid sodium metaaluminate is configured to a concentration of 250g Al2O3/ L sodium aluminate solutions (b).Powdery coconut husk charcoal is added in into sugarcane It is uniformly mixed in sugar aqueous solution, it is 3 that liquid, which consolidates volume ratio,：1, then plus water is beaten, and obtains slurries（c）.Waterglass is according to 1:2 ratio Example dilution in deionized water, is configured to solution (d).A plastic cans, merging 2L deionized waters is taken to add after being heated with stirring to 60 DEG C Enter slurries（c）, open simultaneously have (a), (b) container valve, pH=8.0 of control system, control 45 minutes in will (a) it drips off, closes valve.It is 65 DEG C to keep temperature, pH=8.0, stops after twenty minutes, solution (d) is added in into system, according to The content 55wt% calculating of silica added in 10 minutes in amorphous silica-alumina.Then aging 1 hour, by material in tank into Row filtering is washed to sulfate radical-free ion, is filtered, and filter cake is 10 hours dry at 110 DEG C, obtains catalyst material A-3, so It is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection afterwards, pulverizes and sieves to obtain powder catalyst J-3.Plastic agents useful for same Amount be listed in table 1.
100 grams of catalyst material A-3 is taken, contacts to form paste with the peptization liquid containing nitric acid, extruded moulding, Ran Hou It is 10 hours dry at 110 DEG C, after being roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, impregnated with the maceration extract containing Ce-Fe, so It is 10 hours dry at 110 DEG C afterwards, it is roasted 5 hours under the conditions of 550 DEG C under nitrogen protection, obtains catalyst C.
Above-mentioned synthesis is repeated, catalyst material A-7, powder catalyst J- is made in the not adding carbohydrate during plastic 7th, preformed catalyst G.
1 plastic reagent quality of table
Catalyst Aluminium salt, g Sugar, g Activated carbon, g Cerous nitrate, g Ferric nitrate, g
J-3 144 178 887 130 248
J-7 144 - 887 130 248
Embodiment 1
Certain oil refining enterprise sewage farm uses dual treatment, and wherein the draining of oily waste water treatment series is after bi-membrane method is handled Reuse, the reverse osmosis concentrated water of generation drain into saline sewage processing series.COD is 115mg/L in this burst of concentrated water, and BOD is 0.738mg/L, BOD/COD 0.01, pH=7.5, biodegradability is very poor, influences the up to standard of final outer draining.
Following processing is done to this burst of concentrated water using present invention process：Reverse osmosis concentrated water is adjusted using sodium hydroxide first PH is 11, and processing is filtered using filter, and concentrated water enters one-part form fixed bed catalytic ozonation reactor after filtering, instead Loading catalyst C in device is answered, is passed through ozone.Reaction condition is：Air speed 1h-1, ozone concentration 60g/m3, ozone dosage 120mg/ L concentrated waters.COD is discharged after processing and is reduced to 63mg/L, removal rate 45.2%；BOD is improved to 17.9mg/L, BOD/COD 0.28. After 100 hours, treatment effect does not change continuous operation substantially under the reaction conditions.
Embodiment 2
The reverse osmosis concentrated water water quality that certain oil refining enterprise's reusing sewage generates is as follows：COD is 165mg/L, BOD 8.17mg/L, BOD/COD is 0.05, pH=5.8.This burst of water biodegradability is very poor, and in faintly acid, if directly sent back at sewage farm Reason, it is ineffective.
Following processing is done to this burst of concentrated water using present invention process：The pH of reverse osmosis concentrated water is adjusted using sodium hydroxide first It is 10, processing is filtered using filter, concentrated water enters fixed bed catalytic ozonation reactor after filtering, is filled in reactor Catalyst C is filled out, is passed through ozone.Reaction condition is air speed 1h-1, ozone concentration 60g/m3, ozone dosage 200mg/L concentrated waters.Place COD is discharged after reason and is reduced to 70mg/L, removal rate 57.6%；BOD is improved to 26.7mg/L, BOD/COD 0.38.In the reaction Under the conditions of continuous operation after 100 hours, treatment effect does not change substantially.
Embodiment 3
With embodiment 1, difference is catalytic ozonation reactor loading catalyst G for treatment process and operating condition.After processing Water outlet COD is reduced to 71mg/L, removal rate 38.3%；BOD is improved to 18.4mg/L, BOD/COD 0.26.In the reaction condition After 100 hours, treatment effect does not change lower continuous operation substantially.
Embodiment 4
With embodiment 2, difference is catalytic ozonation reactor loading catalyst G for treatment process and operating condition.After processing Water outlet COD is reduced to 89mg/L, removal rate 46.1%；BOD is improved to 26.8 mg/L, BOD/COD 0.30.In the reaction condition After 100 hours, treatment effect does not change lower continuous operation substantially.
Comparative example 1
With embodiment 1, difference does not adjust pH before being catalytic ozonation for treatment process and operating condition.COD is discharged after processing It is reduced to 80mg/L, removal rate 30%；BOD is improved to 19.3mg/L, BOD/COD 0.24.
Comparative example 2
With embodiment 2, difference does not adjust pH before being catalytic ozonation for treatment process and operating condition.COD is discharged after processing It is reduced to 97mg/L, removal rate 41.2%；BOD is improved to 28.6mg/L, BOD/COD 0.29.
Comparative example 3
With embodiment 1, difference is not add activated carbon during plastic for treatment process and operating condition, and catalyst A is made, Its appearance is white.COD is discharged after processing and is reduced to 93mg/L, removal rate 19.1%；BOD is improved to 15.7mg/L, BOD/COD It is 0.17.Due to not adding activated carbon during plastic, specific surface area is smaller, can not provide enough catalytic active sites Point causes catalyst activity relatively low, therefore bad to COD removal effects in reverse osmosis concentrated water.
Comparative example 4
With embodiment 1, difference is activated carbon 100g used with the peptization liquid containing nitric acid for treatment process and operating condition Contact forms paste, and extruded moulding is then 10 hours dry at 110 DEG C, and roasting 5 is small under the conditions of 550 DEG C under nitrogen protection Shi Hou, obtains carrier, and appearance is black.Then using dipping method supported active metals component, catalyst B is obtained.Processing Water outlet COD is reduced to 65mg/L, removal rate 43.5% afterwards；BOD is improved to 17.8mg/L, BOD/COD 0.27.Comparative example 2 is adopted For catalyst B using activated carbon as carrier, catalyst activity is preferable, to COD removal effects in reverse osmosis concentrated water and 5 base of embodiment This is quite.But its mechanical strength is insufficient, finds that abrasion is more serious during use, powdered carbon is carried in water outlet；In the reaction item After 100 hours, treatment effect decreased significantly continuous operation under part, and catalyst B stability is poor.
From the result of above example and comparative example can be seen that reverse osmosis concentrated water it is processed by the invention after, then through routine Biochemical treatment, it can be ensured that water outlet COD meets discharge standard requirement less than 60mg/L.It is adjusted before filtering using sodium hydroxide solution After the pH of reverse osmosis concentrated water is 10-11, the promotion with obvious effects of catalyst is relatively used alone.The ozone catalyst stability used Good, service life length is, it can be achieved that long-period stable operation.Ozone concentration 4-5g/m3 in tail gas, smelly after catalytic ozonation reaction Coefficient of oxygen utilization is more than 90%, so as to effectively reduce ozone dosage.

Claims (15)

1. a kind of preprocess method for refining oil reverse osmosis concentrated water, it is characterised in that including following content：
（1）Filtration treatment：The pH value for adjusting reverse osmosis concentrated water is 9-13, and filtering removes the suspended matter in reverse osmosis concentrated water；
（2）Catalytic ozonation：Concentrated water carries out catalytic ozonation processing after filtering, and the catalyst includes following nucleocapsids Component, the nucleocapsid component are using activated carbon as core, using the amorphous silica-alumina containing transition metal and rare earth metal as shell, with work On the basis of the weight of property charcoal and amorphous silica-alumina, activated carbon accounts for 10%-70%, and amorphous silica-alumina accounts for 30%-90%；
（3）Stablize processing：Oxidation water outlet enters stabilization pond, decomposes residual ozone in water, enters back into biological treatment system.
2. according to the method described in claim 1, it is characterized in that：Step（1）The pH value of reverse osmosis concentrated water is adjusted to 10- 11。
3. according to the method described in claim 1, it is characterized in that：Step（2）In the catalyst, transition metal is selected from element The base metal in the 4th and 5 periods in periodic table；The rare earth metal is lanthanum, one or more in cerium；The activated carbon Granularity be -300 mesh of 150 mesh.
4. according to the method described in claim 1, it is characterized in that：The amorphous silicon containing transition metal and rare earth metal In aluminium, on the basis of the weight of amorphous silica-alumina, the content of silica is 10%-90%, preferably 30%-70%.
5. according to the method described in claim 1, it is characterized in that：Using transition metal and rare earth metal as active metal component, On the basis of the weight of catalyst, the content of transition metal oxide is 1%-15%, and the content of rare-earth oxide is 1%- 15%, the content of activated carbon and amorphous silica-alumina is 70%-98%.
6. the preparation method of the catalyst of claim 1,3,4 or 5, it is characterised in that including：（1）- 300 mesh of 150 mesh is lived Property charcoal mashing；（2）In the plastic process that amorphous silica-alumina and transition metal and rare-earth metal complex are prepared using coprecipitation Middle introducing step（1）Obtained activated carbon slurries；（3）Step（2）The material after plastic is obtained to carry out aging, be filtered, washed, do It is dry；（4）By step（3）Catalyst is made in the material of gained.
7. according to the method described in claim 6, it is characterized in that：Step（4）By step（3）Catalyst is made in the material of gained At least using one of following methods：
A, by step（3）The material of gained roasts under inert gas shielding, obtains catalyst；
B, by step（3）The material forming of gained after drying, roasts under inert gas shielding, obtains catalyst；
C, by step（3）The material of gained roasts under inert gas shielding, then again through molding, after dry, in inert gas Protection is lower to be roasted, and obtains catalyst.
8. according to the method described in claim 6, it is characterized in that：Step（1）The activated carbon is wood activated charcoal, shell is lived Property charcoal or active carbon from coal；Granularity 150-300 mesh, specific surface area 500-3000m2/ g, hole hold 0.5-1.8cm3/ g, average hole Radius 1-10nm.
9. according to the method described in claim 6, it is characterized in that：Step（1）The activated carbon mashing uses plus water, low-carbon One or more in alcohol are beaten, and wherein low-carbon alcohols are one or more in the monohydric alcohol that carbon atom number is 1-5.
10. according to the method described in claim 6, it is characterized in that：Step（1）Activated carbon is first handled using carbohydrate, Ran Houjin Row mashing；The carbohydrate is the carbohydrate that carbon atom number is 3-20.
11. according to the method described in claim 10, it is characterized in that：The carbohydrate is triose, tetrose, pentose, hexose, wheat One or more in bud sugar, glucose, sucrose, carbohydrate dosage accounts for the 2%-50% of activated carbon weight.
12. the method according to claim 10 or 11, it is characterised in that：The carbohydrate processing activated carbon is that carbohydrate is direct It is mixed with activated carbon or carbohydrate is dissolved in solvent and add activated carbon, solvent therein is water, carbon atom number is 1-5's It is one or more in monohydric alcohol；When carbohydrate handles activated carbon, liquid consolidates volume ratio below 10.
13. according to the method described in claim 6, it is characterized in that：Step（2）Described in coprecipitation prepare amorphous silicon The plastic process of aluminium and transition metal and rare earth metal composite oxide is the neutralization reaction process of acid material and alkaline material, Plastic process is by the way of the continuous acid-base titration of soda acid or in a manner that two kinds of material cocurrents neutralize.
14. according to the method described in claim 1, it is characterized in that：Ozone Oxidation Treatment is reacted using fixed bed catalytic oxidation Device；Ozone is provided by ozone generator, and using oxygen or air as air source, ozone concentration is in 1-150g/m3, ozone dosage exists 30-300mg/L concentrated waters, control catalytic ozonation reaction velocity are 0.1-5/h.
15. it is a kind of for above-mentioned processing method oil refining reverse osmosis concentrated water pretreatment unit, it is characterised in that including filter, Catalytic ozonation reactor and stabilization pond, wherein filter are used to remove the suspended matter in reverse osmosis concentrated water；Concentrated water after filtering It is handled into catalytic ozonation reactor, the catalysis of following nucleocapsid components is filled in catalytic ozonation reactor Agent, the nucleocapsid component are using activated carbon as core, using the amorphous silica-alumina containing transition metal and rare earth metal as shell, with activity On the basis of the weight of charcoal and amorphous silica-alumina, activated carbon accounts for 10%-70%, and amorphous silica-alumina accounts for 30%-90%；After ozone Oxidation Treatment Water outlet enters stabilization pond, makes ozone decomposed remaining in water, enters back into biological treatment system.
CN201611103366.7A 2016-12-05 2016-12-05 A kind of preprocess method and device for refining oil reverse osmosis concentrated water Pending CN108147614A (en)

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