CN102126781B - Method for treating reverse osmosis concentrates of petrochemical wastewater - Google Patents
Method for treating reverse osmosis concentrates of petrochemical wastewater Download PDFInfo
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Abstract
The invention provides a method for treating reverse osmosis concentrates of petrochemical wastewater. The method comprises the following steps: in the presence of a supported metal oxide catalyst, feeding ozone into the reverse osmosis concentrates of the petrochemical wastewater to carry out oxidation reaction, wherein the dosage of ozone is 70-100g/m<3>; the hydraulic load of the catalyst bed is 2-5m3/m<3>.h; the empty tower retention time is 12-20 minutes; the effluent COD is reduced below 50mg/L; the catalyst is formed by using a carrier to support reactive metal oxides; the carrier is selected from activated aluminium oxide or activated carbon; and the reactive metal oxides derive from one or more of manganese nitrate and copper nitrate. By utilizing the complex phase catalytic oxidation method to treat the reverse osmosis concentrates of the petrochemical wastewater with ozone, the method is simple and practical, the cost is low, the method has better treatment effect and the effluent COD can meet the requirement of the emission index.
Description
Technical field
The invention relates to a kind for the treatment of process of petrochemical wastewater reverse osmosis concentrated liquid, specifically refer to handle, make its Pollutant levels to reach the method that emission standard requires to the reverse osmosis concentrated liquid that petrochemical industry refinery waste water reverse osmosis treatment process produces.
Background technology
The application of reverse osmosis method technology in the advanced treatment and reclamation process of refinery waste water is more and more, can produce the concentrated solution of about 30% treatment capacity in the reverse osmosis method treating processes, this its water quality characteristics of class reverse osmosis concentrated liquid has singularity, except the same salt and hardness that contains high density with the reverse osmosis concentrated liquid of general sea water desaltination, particularly also contain and form complicated, very poor organism and the ammonia nitrogen of biological degradability, the general about 120～180mg/L of COD value and ammonia nitrogen sometimes can be up to 50～60mg/L, and the B/C value is less than 0.1 (referring to table 1, table 2).
Table 1 reverse osmosis concentrated liquid water quality analysis measurement result (mg/L)
| Na + | K + | Ca 2+ | Mg 2+ | Al | Fe | Cl - | SO 4 2- | HCO 3 - | CO 3 2- | pH | Ammonia nitrogen | Salinity | COD | BOD | Color |
| 1860 | 42 | 302 | 101 | 0.05 | 0.02 | 1789 | 1858 | 406 | 0 | 6.5 | 53 | 6360 | 180 | 8.8 | Isabelline |
The main water quality parameter measurement result of table 2 reverse osmosis concentrated liquid is concluded
As can be seen, in the reverse osmosis concentrated liquid that refinery waste water reverse osmosis treatment process produces, Pollutant levels must be carried out the processing up to standard of appropriate economy considerably beyond emission standard.
The research bibliographical information that the present reverse osmosis concentrated liquid that produces for this class refinery waste water reverse osmosis treatment process is handled does not seldom have treatment process preferably.
Companies such as U.S. GE propose reverse osmosis concentrated liquid further concentrated and reclaim fresh water, secondary concentration liquid evaporate to dryness, and with the residue landfill that produces or the scheme of burning disposal, this scheme processing cost is too high and be difficult for applying.
In recent years, some preliminary discussions had also been done in domestic processing for refinery waste water reverse osmosis concentrated solution.Liu Dong etc. (" the pressure reducing film distillation method concentrates the reverse osmosis concentrated water experimental study ", water technology, 2009,35 (5): 60-63.) adopt homemade high-throughput PVDF tubular fibre dewatering microporous film, refinery waste water RO concentrated solution is handled by the VMD process, at 70 ℃ of former water temps, vacuum tightness 0.095MPa, flow velocity 0.66ms
-1Condition under, to through reaching 25.83kgm except the VMD process flux of hard pretreated RO concentrated solution
-2H
-1, when being concentrated into 20 times, flux remains on 10kgm
-2H
-1, go out water conductivity and remain on 4 μ Scm
-1Below, ratio of desalinization reaches 99.99%, produces water COD and is stabilized in 35～45mgL
-1Between.Shen Fei etc. (" coagulation-absorption method is handled reverse osmosis concentrated liquid ", in the service water place, 2007,27 (12): 59-62) handle certain petrochemical industry group reverse osmosis concentrated liquid with coagulation/absorption method, investigated the influence of factors such as flocculation agent kind, flocculation agent volume ratio, sorbent material kind, adsorption time, sorbent material consumption, total dosage, pH value and combined treatment mode to the COD removal effect.The result shows, FeCl
3Treatment effect obviously be better than other four kinds of inorganic flocculating agents; FeCl
3The treatment effect that is aided with polymer coagulant aids PAM obviously is better than single FeCl
3The water outlet water white transparency of " coagulation/charcoal absorption " under the certain condition, total COD clearance can reach 56.9%, has reached the petrochemical wastewater secondary discharge standard.The reverse osmosis concentrated draining regeneration of Wang Lianguo etc. (" treatment process research ", Shanxi architecture, 2009,35 (11): 184-185) adopt flocculation → precipitation → fiber filter → ozone BAC process to handle reverse osmosis concentrated liquid, clearance to colourity, ammonia nitrogen, COD is respectively 85%, 53%, 68%, go out total hardness of water below 100mg/L, show that this technology not only can remove most of colourity, ammonia nitrogen and organism in the water, can also remove most of hardness in the water.
But up to the present, still immature to the processing research up to standard of reverse osmosis concentrated liquid, also need do number of research projects.
Summary of the invention
Main purpose of the present invention is to provide a kind for the treatment of process of petrochemical wastewater reverse osmosis concentrated liquid, adopt low-cost, simple technology that the reverse osmosis concentrated liquid that refinery waste water reverse osmosis treatment process produces is handled, reduce COD, make Pollutant levels reach the emission standard requirement.
For reaching above-mentioned purpose, the invention provides a kind for the treatment of process of petrochemical wastewater reverse osmosis concentrated liquid, this method is a kind of ozone complex phase catalytic oxidation, mainly be under the catalyzer existence condition, to adopt the ozone oxidation method that the petrochemical wastewater reverse osmosis concentrated liquid is handled, reduce its COD, make Pollutant levels reach the emission standard requirement.Particularly, the treatment process of petrochemical wastewater reverse osmosis concentrated liquid of the present invention comprises:
In the presence of the load metal oxide catalyzer, feed ozone in the petrochemical wastewater reverse osmosis concentrated liquid and carry out oxidizing reaction, ozone dosage 70～100g/m
3, the hydraulic load 2～5m of beds
3/ m
3H, the void tower residence time 12～20min can make water outlet COD be reduced to below the 50mg/L.
According to specific embodiments of the present invention, in the treatment process of petrochemical wastewater reverse osmosis concentrated liquid of the present invention, described catalyzer is made of the supported carrier active metal oxide, described carrier is selected from activated alumina or gac, and described active metal oxide is derived from one or more in manganous nitrate, the cupric nitrate.Preferably, described active metal oxide is the copper-manganese oxide compound, and described active metal oxide is derived from manganous nitrate and cupric nitrate.More preferably, described copper-manganese mass ratio 3～6: 1, most preferably mass ratio is 3～5: 1, has good catalytic performance for the oxidative degradation of ozone Oxidation Treatment refinery reverse osmosis concentrated liquid.
According to specific embodiments of the present invention, in the treatment process of petrochemical wastewater reverse osmosis concentrated liquid of the present invention, the loading 2wt%～8wt% of active metal oxide in the described catalyzer.
According to specific embodiments of the present invention, in the treatment process of petrochemical wastewater reverse osmosis concentrated liquid of the present invention, described catalyzer prepares in accordance with the following methods:
Blank carrier joined in the certain density active constituent liquid flood, dry, roasting afterwards or oxygen barrier roasting obtain finished catalyst; Wherein, 300 ℃～500 ℃ of described maturing temperatures are preferably greater than 400 ℃ smaller or equal to 500 ℃.
According to specific embodiments of the present invention, in the treatment process of petrochemical wastewater reverse osmosis concentrated liquid of the present invention, the carrier particle diameter has very big influence to the catalyst oxidation susceptibility, and preferred described carrier particle diameter is 2～5mm, more preferably 2～3mm among the present invention.The catalytic oxidation performance of the catalyzer of carrier particle diameter 2～3mm is the catalyzer of 3～5mm significantly better than the carrier particle diameter.
According to specific embodiments of the present invention, in the treatment process of petrochemical wastewater reverse osmosis concentrated liquid of the present invention, the initial pH value of controlling described petrochemical wastewater reverse osmosis concentrated liquid is 5～11, is preferably 7～9.The O of refinery reverse osmosis concentrated liquid of the present invention
3The complex phase catalytic oxidation, the oxygenolysis effect under acid and neutrallty condition is better than alkaline condition.
The treatment process of petrochemical wastewater reverse osmosis concentrated liquid of the present invention, can be adopt static, step operation is handled the petrochemical wastewater reverse osmosis concentrated liquid, also can be to adopt the operation of dynamic continous way to handle.For example, in a specific embodiments of the present invention, the treatment process of petrochemical wastewater reverse osmosis concentrated liquid of the present invention comprises step:
Ozone complex phase catalyst oxidation reactor is set, loading catalyst bed in this reactor, pending petrochemical wastewater reverse osmosis concentrated liquid passes through beds from top to bottom from the reactor upper end, utilize ozonizer in reactor, to feed ozone simultaneously, make ozone from bottom to top by beds, the gas-liquid counter current contact reacts; Wherein, ozone dosage 70～100g/m
3, the hydraulic load 2～5m of beds
3/ m
3H, the void tower residence time 12～20min;
Water liquid after the processing is drawn from reactor bottom, and gas phase is drawn recovery from reactor head.
Utilize ozone complex phase catalytic oxidation of the present invention to handle the petrochemical wastewater reverse osmosis concentrated liquid, method is simple, and has treatment effect preferably, and water outlet COD can reach the requirement of discharge index.The present invention has also carried out on-the-spot pilot scale Processing Test to the petrochemical wastewater reverse osmosis concentrated liquid, show through the operation result of a wheat harvesting period, limpid colourless, the COD of water outlet can be basicly stable at＜50mg/L, and running cost≤2.33 yuan/ton water.
Description of drawings
Fig. 1 shows the oxidation effectiveness under carrier free, the blank carrier situation.
Fig. 2 shows that the different maturing temperatures Mn catalyst that places an order handles the COD degradation rate of petrochemical wastewater reverse osmosis concentrated liquid.
Fig. 3 shows the oxidation effectiveness of different copper-manganese catalyst component ratios.
Fig. 4 shows the ozone-depleting amount contrast of single Mn catalyst and copper-manganese catalyst treatment petrochemical wastewater reverse osmosis concentrated liquid.
Fig. 5 shows the catalyzed oxidation effect of catalyzer ZYW-1 under the different water sample initial pH value.
Fig. 6 shows tail gas ozone concn under the different water sample initial pH value.
Fig. 7 shows that the different carriers particle diameter is to the influence of COD degradation rate and with the variation in reaction times.
Fig. 8 is on-the-spot pilot plant test schematic flow sheet among the embodiment 5.
Embodiment
Further describe treatment process of the present invention and obtained technique effect below by specific embodiment, but therefore the present invention is not subjected to any restriction.
The preparation of embodiment 1, single Mn catalyst and use it and carry out reverse osmosis concentrated liquid ozone complex phase catalytic oxidation treatment
1, the preparation of single Mn catalyst
Prepare certain density manganese nitrate solution, (particle diameter 3～5mm) floods with above-mentioned solution dry method, and steeping fluid blots substantially to get 150 gram alumina supporters; After placing 12 hours airings, again through 80 ℃ dry 12 hours down, roasting at a certain temperature is 4 hours then, then nitrate is decomposed into metal oxide, and is bonded on the carrier, makes the solid catalyst finished product, the catalyst activity component loading of producing is 6%.
In the present embodiment, respectively 300 ℃, 400 ℃, 450 ℃, 500 ℃ following roastings, prepare the single Mn catalyst finished product under the different maturing temperatures.
2, reverse osmosis concentrated liquid ozone complex phase treatment by catalytic oxidation
The Carberry gradientless reactor is adopted in experiment, and catalyst reactor places the rotation basket that has sieve aperture.During experiment, at first 150 gram catalyzer are packed in the catalyst basket, be connected with agitator, then the 3L water sample is added reactor, it is 50L/hr that the adjustments of gas under meter makes air flow, turn on agitator, and the catalyst basket rotating speed is 100r/min, stable back is opened ozonizer and is picked up counting simultaneously, and timing sampling is measured.
For the katalysis of the metal oxide that clearly shows load, at first investigated the result of blank assay in the present embodiment.Blank assay in two kinds of situation, carrier free is reaction and the gas-liquid-solid phase reaction in the presence of blank carrier of simple gas-liquid two-phase.Experimental result is seen Fig. 1.
As seen from Figure 1, in the entire reaction course, blank carrier is higher than carrier free to the influence of COD degraded, the former degradation rate 70.6% of 8 hours, and the latter is 65.9%, this explanation carrier has certain katalysis to ozone oxidation.
Figure 2 shows that single Mn catalyzer of making in the present embodiment is to the influence of oxidation effectiveness under different maturing temperatures (300 ℃, 400 ℃, 450 ℃, 500 ℃).
As seen from Figure 2, the single Mn catalyst initial reaction speed for preparing under four maturing temperatures is fast, and along with the prolongation in reaction times, COD constantly reduces, and speed of response also slows down; The COD degradation rate of four catalyzer is more or less the same after 8 hours, is respectively 69%, 68.7%, 67.5% and 66.5%.From experimental data, the catalyzer of 300 ℃ and 400 ℃ following roastings is a little better, but find in the evaluation procedure, the catalyzer of 300 ℃ and 400 ℃ following roastings oxide compound active ingredient when estimating has obscission, so, maturing temperature preferably is not less than 400 ℃, most preferably greater than 400 ℃ smaller or equal to 500 ℃.
The preparation of embodiment 2, copper manganese bicomponent catalyst and use it and carry out reverse osmosis concentrated liquid ozone complex phase catalytic oxidation treatment
In single Mn catalyzer, infiltrate some copper components, preparation copper manganese bicomponent catalyst.In the copper-manganese ratio, prepare certain density manganous nitrate and cupric nitrate mixing solutions, (particle diameter 3～5mm) floods with above-mentioned solution dry method, and steeping fluid blots substantially to get 150 gram absorbent charcoal carriers; After placing 12 hours airings, again through 80 ℃ dry 12 hours down, 450 ℃ of roasting temperatures 4 hours, then nitrate was decomposed into metal oxide, and is bonded on the carrier, makes the solid catalyst finished product then, the catalyst activity component loading of producing is 6%.
In the present embodiment, utilize prepared copper manganese bicomponent catalyst to carry out reverse osmosis concentrated liquid ozone complex phase catalytic oxidation treatment, the adding of investigation copper in single Mn catalyzer and add-on are to the influence of oxidation effectiveness.Experimental technique is with embodiment 1.
The results are shown in Figure 3.As can be seen from Figure 3, the variation of copper-manganese ratio has certain influence to the COD clearance, and comparatively speaking, the effect of 3: 1 (mass ratio) catalysts of copper-manganese preferably and 6: 1 (mass ratio) catalyzer of copper-manganese are the poorest.
The contrast of ozone-depleting amount when Fig. 4 has shown single Mn catalyst of 450 ℃ of following roastings among the embodiment 1 and the copper-manganese catalyst treatment petrochemical wastewater reverse osmosis concentrated liquid in the present embodiment, in the tail gas ozone concn higher relatively be that ozone-depleting is relatively low.The copper-manganese catalyzer has treatment effect preferably than single Mn catalyst as can be seen.
Carry out reverse osmosis concentrated liquid ozone complex phase catalytic oxidation treatment under embodiment 3, the initial pH condition of different water sample
Select 3: 1 (mass ratio) catalyzer of copper-manganese of embodiment 2 preparations, brief note ZYW-1.Regulating the water sample initial pH value with sodium hydroxide or sulphuric acid soln respectively is 5,7 and 11, carries out reverse osmosis concentrated liquid ozone complex phase catalytic oxidation treatment, the results are shown in table 3 and Fig. 5, Fig. 6.As can be seen, the degradation rate of water sample initial pH value COD under acid and neutrallty condition is more or less the same, though slightly high than the degradation rate under the alkaline condition, differ remarkable (see Table 3, Fig. 5).On the ozone-depleting amount, alkalescence is O down
3Consumption to be far longer than acid and neutral O down
3The consumption (see figure 6), acid and neutral O down
3Consumption suitable substantially.Obviously, catalyzer has catalytic activity preferably under acidity or neutrallty condition, considering that metal oxide catalyst moves under acidic conditions causes loss of active component easily, on the other hand, reverse osmosis concentrated liquid is in neutral meta-alkalescence (pH6.5～8) substantially, therefore, pH value that in use can uncomfortable water saving sample.
Table 3 initial pH value is to the influence of catalyzer ZYW-1 catalytic ozonation effect
Present embodiment has selected for use the identical particle diameter of material to be respectively the absorbent charcoal carrier of 2～3mm and 3～5mm, and the method according to embodiment 2 prepares catalyzer ZYW-1 (copper-manganese mass ratio 3: 1) respectively, investigates particle diameter to the influence of oxide treatment effect.In 1 hour reaction times, the initial pH value of water sample is 7, catalytic additive amount 150 grams, and volume of water sample is 3L, and experimental result sees Table 4, and the IO in the table is the ozone index, the ozone amount (mg) that representation unit COD degradation amount (mg) consumes.
The influence of table 4 carrier particle diameter (1 hour reaction times)
| Reaction system | COD degradation rate (%) | O 3Consumption (mg) | IO |
| Carrier (3～5mm) | 21.9 | 1204 | 3.13 |
| Carrier (2～3mm) | 30.2 | 918 | 1.72 |
| ZYW-1(3～5mm) | 24.3 | 1214 | 2.73 |
| ZYW-1(2～3mm) | 36.6 | 836 | 1.17 |
As can be seen from Table 4, the size of carrier particle diameter is very big to the catalyst performance influence, carrier (2～3mm) than carrier (3～5mm) effective, the COD degradation rate exceeds 8.3%, and the ozone amount that consumes has lacked 286 milligrams, the IO value is reduced to 1.72 from 3.13, has reduced 1.41, and (3～5mm) effect is not bad than ZYW-1.ZYW-1 (2～3mm) than ZYW-1 (3～5mm) effective a lot, the ozone-depleting amount reduces 378 milligrams when the COD degradation rate has exceeded 12.3%, ozone index IO is reduced to 1.17 from 2.73, has reduced 1.56.As seen, the small particle size carrier has better catalytic performance than big particle diameter carrier.
Be catalyzer with ZYW-1, under neutrallty condition, investigate with the influence to the ozone oxidation effect of the catalyzer of different-grain diameter preparing carriers, the results are shown in Table 5 and Fig. 7.Comparison sheet 5 and Fig. 7 as can be known, the small particle size catalyzer is more effective than big particle size of catalyst, it is high about 11%～13% that degradation rate is wanted basically, the former reaches 72.0% at 5 hours COD degradation rate, the latter reaches same degradation rate needs 7 to 8 hours.
Table 5 carrier particle diameter is to the influence of catalyst activity
On-the-spot pilot plant test water inlet is extracted from the reverse osmosis unit drainage tray.Pilot plant test lasts 38 days from the 2010.11.21-2010.12.28 commencement of commercial operation.ZYW-1 (2～3mm) catalyst levels 220kg, the about 400L of stacking volume; The ozonizer model is CF-G-2-300 (Qingdao state woods Industrial Co., Ltd. produces, air source, maximum generating capacity 300g/hr).Fixed-bed reactor total height 3.10m, diameter 0.5m, catalyst bed layer height: 2.15m.On-the-spot pilot plant test schematic flow sheet is referring to Fig. 8.
Operational condition:
Liquid level: 2.3m, flooding velocity: 1.0～1.5m
3/ h, the void tower residence time: 12.6～16.8min, hydraulic load: 2.38～3.57m
3/ (m
3.h), air flow quantity: 9.5m
3/ h, ozonizer operating power: 4.5～6kW, actual ozone dosage 70～100g/m
3
On-the-spot pilot plant test result:
Duration of test if the monitoring Inlet and outlet water the COD value, the COD pH-value determination pH carries out at petro-chemical corporation analytical test center, every morning and afternoon each sampling and measuring once.Table 6 has provided the COD monitoring result of pilot plant test.
Several days initial stage that brings into operation, flooding velocity was 1.0m
3/ h, since November 25 to off-test, flooding velocity is adjusted to 1.5m
3/ h, at this moment, the void tower residence time is 16.8min, hydraulic load is 3.75m
3/ (m
3.h).Under the certain situation of air flow quantity, ozone concn is decided by the operating power of ozonizer in ozone generation amount or the ozonized air, is the linear changing relation between generation and the power substantially.Began several days, ozonizer moves with full power, and November 26 rose to December 16, and operating power is stabilized in 5.6kW～5.7kW, and December 17 was further turned down 4.5kW. with power to off-test.
During whole pilot plant test, water inlet (reverse osmosis concentrated liquid) COD fluctuates in about 100～135mg/L scope substantially.
The COD monitoring result of table 6 pilot plant test
As can be known from the results of Table 6, at the initial stage that brings into operation, because the adsorption of support of the catalyst, water outlet COD value is very low, moved about 10 days after, water outlet COD value tends towards stability substantially, greatly about 38～45mg/L, on average greatly about about 42mg/L; From December 17, the operating power of ozonizer is turned down to 4.5kW, water outlet COD raises to some extent but maintains＜50mg/L, greatly between 41～49mg/L, on average greatly about 46mg/L.
Ozone complex phase catalytic oxidation process consumes main ozoniferous electric energy, does not consume pharmaceutical chemicals basically, and therefore, the running cost of ozone complex phase catalytic oxidation process mainly is exactly ozoniferous power consumption.According to the pilot-scale experiment of table 6, can guard a consideration and get operating power 5.0kW, per hour consume the electric energy of 5kWh, flooding velocity is 1.5m
3/ h, the price of electricity is got 0.70 yuan/kWh.Therefore, running cost is: 5kWh/1.5m
3/ h * 0.70 yuan/kWh=2.33 unit/ton water.
Operation result through on-the-spot pilot plant test one wheat harvesting period shows, limpid colourless, the COD of water outlet can be basicly stable at＜50mg/L.
The contriver also adopts the method for prior art that embodiment 5 identical petrochemical wastewater reverse osmosis concentrated liquids are handled, to compare with the result of utilizing ozone complex phase catalytic oxidation of the present invention in research process.Wherein:
1, Coagulation with Treatment does not have effect substantially to the removal of huge port petrochemical wastewater reverse osmosis concentrated liquid COD.Know by inference from the precipitation experimental result, the calcium ion in the concentrated solution has a very big part to exist with the form of the more stable inner complex of chemical property, makes the COD removal of reverse osmosis concentrated liquid and hard-off processing all increase difficulty.
2, charcoal absorption can be removed the COD material of reverse osmosis concentrated liquid, the COD of absorption back water outlet is reached＜the discharge index requirement of 50mg/L, but adsorptive capacity is too low, and only about 10mg/g gac will make running cost too high.
3, the top condition of two-dimensional electrode electrochemical oxidation process processing reverse osmosis concentrated liquid is: anode adopts Ti/RuO
2-IrO
2-TiO
2Anode, voltage are 13V, and distance between plates is 10mm, and aeration rate is 40L/h, and salinity is 9000mg/L, the COD of reverse osmosis concentrated liquid behind the oxidation 45min
CrReduce to 50.1mg/L, clearance has reached 68.9%, and ammonia nitrogen is reduced to 0.25mg/L, and clearance has reached 99.5%, yet treatment operating costs is 8～10 yuan/side, far above method of the present invention.
4, UV/Fenton oxidation, O
3And UV/O
3Oxidation pre-treatment huge port petrochemical wastewater reverse osmosis concentrated liquid can make the B/C value of concentrated solution from bringing up to 0.5～0.6 significantly less than 0.1.But experimental result shows, the biological treatment effect of concentrated solution that has improved the B/C value is bad, and COD removes not high, is difficult to make that to handle the direct oxidation of back water outlet COD value up to standard, reaches discharge index and requires relatively more difficult.
Claims (9)
1. the treatment process of a petrochemical wastewater reverse osmosis concentrated liquid, this method comprises:
In the presence of the load metal oxide catalyzer, feed ozone in the petrochemical wastewater reverse osmosis concentrated liquid and carry out oxidizing reaction, ozone dosage 70～100g/m
3, the hydraulic load 2～5m of beds
3/ m
3H, the void tower residence time 12～20min is reduced to below the 50mg/L water outlet COD;
Wherein, described catalyzer is made of the supported carrier active metal oxide, and described carrier is selected from activated alumina or gac; Described metal oxide is the copper-manganese oxide compound, copper-manganese mass ratio 3～6: 1.
2. the treatment process of petrochemical wastewater reverse osmosis concentrated liquid according to claim 1, wherein, the loading of active metal oxide is 2wt%～8wt% in the described catalyzer.
3. the treatment process of petrochemical wastewater reverse osmosis concentrated liquid according to claim 1, wherein, described catalyzer prepares in accordance with the following methods:
Blank carrier joined in the certain density active constituent liquid flood, dry, roasting afterwards or oxygen barrier roasting obtain finished catalyst; Wherein, described maturing temperature is 300 ℃～500 ℃.
4. the treatment process of petrochemical wastewater reverse osmosis concentrated liquid according to claim 3, wherein, described maturing temperature greater than 400 ℃ smaller or equal to 500 ℃.
5. the treatment process of petrochemical wastewater reverse osmosis concentrated liquid according to claim 1, wherein, described carrier particle diameter is 2～5mm.
6. the treatment process of petrochemical wastewater reverse osmosis concentrated liquid according to claim 1, wherein, described carrier particle diameter is 2～3mm.
7. the treatment process of petrochemical wastewater reverse osmosis concentrated liquid according to claim 1, wherein, the initial pH value of controlling described petrochemical wastewater reverse osmosis concentrated liquid is 5～11.
8. the treatment process of petrochemical wastewater reverse osmosis concentrated liquid according to claim 1, wherein, the initial pH value of controlling described petrochemical wastewater reverse osmosis concentrated liquid is 7～9.
9. the treatment process of petrochemical wastewater reverse osmosis concentrated liquid according to claim 1, the method comprising the steps of:
Ozone complex phase catalyst oxidation reactor is set, loading catalyst bed in this reactor, pending petrochemical wastewater reverse osmosis concentrated liquid passes through beds from top to bottom from the reactor upper end, utilize ozonizer in reactor, to feed ozone simultaneously, make ozone from bottom to top by beds, the gas-liquid counter current contact reacts; Wherein, ozone dosage 70～100g/m
3, the hydraulic load 2～5m of beds
3/ m
3H, the void tower residence time 12～20min;
Water liquid after the processing is drawn from reactor bottom, and gas phase is drawn recovery from reactor head.
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| CN102923894B (en) * | 2012-10-30 | 2014-04-30 | 北京理工大学 | Process and device for treating reverse osmosis concentrated water through dual-membrane distillation |
| CN104445764A (en) * | 2014-11-24 | 2015-03-25 | 青岛青科金诺环境工程技术有限公司 | Catalysis-ozone oxidation treatment method and device for salt-containing degradation-resistant organic wastewater |
| CN105080523A (en) * | 2015-07-23 | 2015-11-25 | 武汉钢铁(集团)公司 | Preparation method for catalyst in catalytic ozonation for treating organic matter-containing wastewater |
| CN105731629A (en) * | 2016-02-19 | 2016-07-06 | 博天环境集团股份有限公司 | Catalytic oxidation treatment method of reverse-osmosis strong brine |
| CN106565036A (en) * | 2016-11-11 | 2017-04-19 | 大连理工大学 | Method for catalytic ozonation and COD and total nitrogen removal from waste water at same time |
| CN113666543A (en) * | 2021-09-16 | 2021-11-19 | 上海泓济环保科技股份有限公司 | Reverse osmosis concentrated water treatment process for strengthening activated carbon adsorption through catalytic oxidation of ozone |
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