CN105731629A - Catalytic oxidation treatment method of reverse-osmosis strong brine - Google Patents
Catalytic oxidation treatment method of reverse-osmosis strong brine Download PDFInfo
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- CN105731629A CN105731629A CN201610094307.1A CN201610094307A CN105731629A CN 105731629 A CN105731629 A CN 105731629A CN 201610094307 A CN201610094307 A CN 201610094307A CN 105731629 A CN105731629 A CN 105731629A
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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
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/784—Diffusers or nozzles for ozonation
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The embodiment of the invention discloses a catalytic oxidation treatment method of reverse-osmosis strong brine. The method includes the following steps of measuring the pH value of reverse-osmosis strong brine, introducing reverse-osmosis strong brine into an ozone contact oxidation tower when the pH value of reverse-osmosis strong brine is 2 to 10, adding compound multi-element oxidant into the tower, and conducting sufficient contact reaction on reverse-osmosis strong brine, continuous aeration ozone, a liquid ozone oxide catalyst and compound multi-element oxidant in the ozone contact oxidation tower for 10-80 minutes. The ozone contact oxidation tower is designed vertically, a water inlet is formed in the upper portion of the tower, a water outlet is formed in the lower portion of the tower, an ozone aeration head is arranged at the bottom of the tower, a bearing layer is arranged in the tower and filled with an ozone oxidation catalyst, and an addition opening of compound multi-element oxidant is formed in the outer wall of the tower. By means of the method, the mass transfer effect of gas, liquid and solid is enhanced, and the catalysis efficiency of the ozone oxidation catalyst is greatly improved.
Description
Technical field
The present invention relates to technical field of waste water processing, particularly to the treatment by catalytic oxidation of a kind of reverse osmosis concentrated saline.
Background technology
Reverse osmosis technology is the feature utilizing reverse osmosis membrane to have selective penetrated property, is filtered concentration to surface water or through the sewage of advanced treating, filters the salt in water, Organic substance and other granule foreign, it is achieved the purpose of purification of water quality or Treated sewage reusing.Producing substantial amounts of strong brine in reverse-osmosis treated process, and the strong brine water yield generally accounts for the 1/3 of the reuse water yield, not treated direct discharge can cause the waste of water resource, also will surrounding be polluted simultaneously.Therefore, reverse osmosis concentrated saline is recycled, seemed particularly urgent.
Ozone technology is the Sewage advanced treatment technology of current international mainstream.This technology oxidability is strong, and reaction rate is fast, and occupation area of equipment is little, can not only be used for individual processing, with other processing procedure couplings, can reduce processing cost again.But single ozone oxidation has certain limitation, it is therefore desirable to improve the oxidation efficiency of ozone by ozone oxidation catalyst.But the ozone oxidation catalyst of the fixing bed of routine is seated in inside O3 contacted oxidation tower with the form piled up, and causes that the catalytic effect of ozone oxidation catalyst is poor.
Summary of the invention
The embodiment of the invention discloses the treatment by catalytic oxidation of a kind of reverse osmosis concentrated saline, the problem poor for solving the catalytic effect of ozone oxidation catalyst.Technical scheme is as follows:
The treatment by catalytic oxidation of a kind of reverse osmosis concentrated saline, comprises the following steps:
Measure the pH value of reverse osmosis concentrated saline；
When the pH value of reverse osmosis concentrated saline is 2～10, reverse osmosis concentrated saline is passed in O3 contacted oxidation tower, composite multi-component oxidant is added in described O3 contacted oxidation tower, described reverse osmosis concentrated saline carries out being fully contacted reaction with the ozone of continuous aeration, fluidization ozone oxidation catalyst and composite multi-component oxidant in described O3 contacted oxidation tower, and the response time is 10～80min；
Described O3 contacted oxidation tower adopts upright type of design, its top is provided with water inlet, bottom is provided with outlet, bottom is provided with ozonation aerated head, for providing the ozone of continuous aeration, it is provided with supporting layer in O3 contacted oxidation tower, described supporting layer is filled with ozone oxidation catalyst, the outer wall of described O3 contacted oxidation tower is provided with the dosing mouth of composite multi-component oxidant；
Specific surface area >=the 300m of described ozone oxidation catalyst2/ g, bulk density is 0.11～0.17g/ml, and dosage is 200～1000mg/L；
Described ozone oxidation catalyst meets fluidised parameter: the particle diameter of described ozone oxidation catalyst is 0.3～0.5mm, comprcssive strength > 160N, wear rate≤0.1%W；
Described ozone dosage is 50～500mg/L；
Described composite multi-component oxidant, including: one or more in persulfate, hydrogen peroxide, calper calcium peroxide, sodium hypochlorite, calcium hypochlorite, chlorine dioxide.
In the preferred embodiment of the present invention, when the pH value of reverse osmosis concentrated saline is 6～9, reverse osmosis concentrated saline is passed in O3 contacted oxidation tower.
One in the present invention is more highly preferred in embodiment, described ozone oxidation catalyst, including: carrier material and active component；Wherein, described carrier material includes: the one in granular porous aluminium oxide ceramic, granulated activated, particulate molecular sieve, coal-based column-shaped active carbon, graininess active fruit shell carbon, graininess many silicon clinoptilolite；Described active component is one or more in manganese, nickel, ferrum, cerium, cobalt, copper.
One in the present invention is more highly preferred in embodiment, and described persulfate includes: one or more in Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate.
One in the present invention is more highly preferred in embodiment, and the dosage of described composite multi-component oxidant is 30～300mg/L.
One in the present invention is more highly preferred in embodiment, and the mass ratio of described ozone and composite multi-component oxidant is 2:3～5:1.
One in the present invention is more highly preferred in embodiment, and the dosing mouth of described composite multi-component oxidant is arranged in described O3 contacted oxidation tower 1/4 place of liquid level, 2/4 place, 3/4 place, 4/4 place.
One in the present invention is more highly preferred in embodiment, and described composite multi-component oxidant uniformly adds at four dosing mouths simultaneously.
One in the present invention is more highly preferred in embodiment, and described O3 contacted oxidation tower also includes internal circulation apparatus；
Described treatment by catalytic oxidation also includes: starting circulating pump, the reverse osmosis concentrated saline in described O3 contacted oxidation tower is circulated process, described quantity of circulating water is the 10%～50% of inflow.
The treatment by catalytic oxidation of a kind of reverse osmosis concentrated saline provided by the invention, by controlling the flow of ozone continuous aeration, realize the steady flow condition of ozone oxidation catalyst, strengthen the mass transfer effect between gas, liquid, solid three-phase, the catalytic efficiency of ozone oxidation catalyst is greatly improved.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, the accompanying drawing used required in embodiment or description of the prior art will be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
The schematic flow sheet of the treatment by catalytic oxidation of a kind of reverse osmosis concentrated saline that Fig. 1 provides for the embodiment of the present invention；
Fig. 2 is the structural representation of the O3 contacted oxidation tower in method shown in Fig. 1.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
The schematic flow sheet of the treatment by catalytic oxidation of a kind of reverse osmosis concentrated saline that Fig. 1 provides for the embodiment of the present invention, comprises the following steps:
S1: measure the pH value of reverse osmosis concentrated saline；
S2: when the pH value of reverse osmosis concentrated saline is 2～10, reverse osmosis concentrated saline is passed in O3 contacted oxidation tower, composite multi-component oxidant is added in described O3 contacted oxidation tower, described reverse osmosis concentrated saline carries out being fully contacted reaction with the ozone of continuous aeration, fluidization ozone oxidation catalyst and composite multi-component oxidant in described O3 contacted oxidation tower, and the response time is 10～80min.
When the pH value of reverse osmosis concentrated saline is not 2～10, first regulates the pH value of reverse osmosis concentrated saline to 2～10 with acid or alkali, then the more reverse osmosis concentrated saline mixing up pH value is passed in O3 contacted oxidation tower.In a preferred embodiment of the present invention, when the pH value of reverse osmosis concentrated saline is 6～9, reverse osmosis concentrated saline is passed in O3 contacted oxidation tower.
The structure of described O3 contacted oxidation tower, as in figure 2 it is shown, described O3 contacted oxidation tower adopts upright type of design, is provided with supporting layer, described supporting layer is filled with ozone oxidation catalyst in tower；O3 contacted oxidation tower bottom is provided with ozonation aerated head, for providing the ozone of continuous aeration；O3 contacted oxidation tower top is provided with water inlet, and water inlet is higher than ozone oxidation catalyst top；Bottom is provided with outlet, outlet position between ozonation aerated device and supporting layer；The outer wall of O3 contacted oxidation tower is provided with the dosing mouth of composite multi-component oxidant.
Specific surface area >=the 300m of described ozone oxidation catalyst2/ g, bulk density is 0.11～0.17g/ml, and dosage is 200～1000mg/L.
In experimentation, inventor have found that when the particle diameter of described ozone oxidation catalyst is 0.3～0.5mm, comprcssive strength > 160N, during wear rate≤0.1%W, the flow of ozone continuous aeration can be regulated according to practical situation, make ozone oxidation catalyst present stable flow regime.The present invention stable flow regime said here can be understood as particulate fluidization state, and the feature of particulate fluidization state is that solid particle is dispersed in the fluid of flowing and has a stable upper interface.In this state, being fully contacted between reverse osmosis concentrated saline, ozone and ozone oxidation catalyst three, the mass transfer effect between gas, liquid, solid three-phase significantly improves, thus the catalytic efficiency of ozone oxidation catalyst is greatly improved.Wherein, described ozone dosage is 50～500mg/L.Described ozone oxidation catalyst, including: carrier material and active component.Inventor have found that, when carrier material includes: the one in granular porous aluminium oxide ceramic, granulated activated, particulate molecular sieve, coal-based column-shaped active carbon, graininess active fruit shell carbon, graininess many silicon clinoptilolite；When active component is one or more in manganese, nickel, ferrum, cerium, cobalt, copper, described ozone oxidation catalyst has good catalytic oxidation effect.
For the ozone oxidation catalyst adopted in technical scheme, those skilled in the art can according to the present invention in this published parameter, for instance size, comprcssive strength, wear rate etc., selects commercially available various ozone oxidation catalysts；Additionally, have been reported that owing to catalytic ozonation technology more, the preparation method of its corresponding catalyst is also a lot, therefore those skilled in the art can also adopt prior art to prepare relevant catalyst according to the carrier material of the catalyst that disclosed in this invention and active component, this is easily realize to those skilled in the art, and the present invention does not specifically limit at this.
Adding composite multi-component oxidant in O3 contacted oxidation tower, synergy ozone aoxidizes the Organic substance in reverse osmosis concentrated saline, oxidation effect.Preferably, when reverse osmosis concentrated saline is passed in O3 contacted oxidation tower, composite multi-component oxidant is also added in O3 contacted oxidation tower simultaneously.Described composite multi-component oxidant, including: one or more in persulfate, hydrogen peroxide, calper calcium peroxide, sodium hypochlorite, calcium hypochlorite, chlorine dioxide；Wherein, described persulfate includes: one or more in Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate.Described composite multi-component oxidant joins in O3 contacted oxidation tower by the dosing mouth of O3 contacted oxidation tower outer wall, and dosing mouth is arranged on 1/4 place of liquid level in O3 contacted oxidation tower, 2/4 place, 3/4 place, 4/4 place.Inventor have found that described composite multi-component oxidant is when four dosing mouths uniformly add simultaneously, the treatment effect obtained is more excellent.In experimentation, the inventors have also found that the synergistic oxidation effect of composite multi-component oxidant is preferably when the dosage of described composite multi-component oxidant is 30～300mg/L；When the mass ratio of described ozone and composite multi-component oxidant is 2:3～5:1, the synergistic oxidation best results of composite multi-component oxidant.
In treatment by catalytic oxidation provided by the invention, described O3 contacted oxidation tower can also include internal circulation apparatus.When O3 contacted oxidation tower includes internal circulation apparatus, those skilled in the art can start circulating pump, and the reverse osmosis concentrated saline in O3 contacted oxidation tower is circulated process, with the effect that reinforcement processes.Internal recycle design will flow to the reverse osmosis concentrated saline of O3 contacted oxidation tower bottom by circulating pump, force to extract the top flowing into O3 contacted oxidation tower, it is achieved the circulation of current, increase the process of catalytic oxidation treatment, the effect of fortifying catalytic oxidation processes.Described quantity of circulating water is the 10%～50% of inflow.
Following by specific embodiment, the present invention is described in detail.
Embodiment 1
Waste water takes from certain reverse osmosis concentrated saline of refinery project of Poten Environment Group Co., Ltd..The initial water quality index of waste water: CODCr(adopt potassium dichromate (K2Cr2O7) chemical oxygen consumption (COC) (ChemicalOxygenDemand) that determines as oxidant) for 303.7mg/L, colourity is 64 times, and turbidity is 1.285NTU.
Taking 1L waste water, measure the pH value of waste water, pH value is 7.4.In O3 contacted oxidation tower, add the graininess active fruit shell carbon supported on carriers that 0.3g particle diameter is 0.3mm have the ozone oxidation catalyst of manganese, nickel, pass into ozone at O3 contacted oxidation tower bottom and carry out continuous aeration, ozone flow is 0.80L/min, dosage is 360mg, in the case, ozone oxidation catalyst presents stable flow regime.100mg hydrogen peroxide is split the quartering, uniformly adds in four dosing mouths of O3 contacted oxidation tower outer wall simultaneously.Being passed in O3 contacted oxidation tower from the water inlet of O3 contacted oxidation tower by waste water and react, the response time is 35min.
After reaction terminates, collect water outlet from the outlet of O3 contacted oxidation tower, measure the water quality of water outlet.Water outlet CODCrFor 27.6mg/L, colourity is 2 times, and turbidity is 0.26NTU.Waste water after treatment, CODCrClearance be 90.9%, the clearance of colourity is 96.9%, and the clearance of turbidity is 79.8%.
Embodiment 2
Waste water takes from certain reverse osmosis concentrated saline of refinery project of Poten Environment Group Co., Ltd..The initial water quality index of waste water: CODCrFor 298.4mg/L, colourity is 64 times, and turbidity is 1.296NTU.
Taking 2L waste water, measure the pH value of waste water, pH value is 6.5.Adding 1g particle diameter in O3 contacted oxidation tower is the ozone oxidation catalyst being loaded with ferrum, nickel, copper on the granular porous pottery of 0.5mm, pass into ozone at O3 contacted oxidation tower bottom and carry out continuous aeration, ozone flow is 1.20L/min, dosage is 474mg, in the case, ozone oxidation catalyst presents stable flow regime.400mg sodium hypochlorite is split the quartering, uniformly adds simultaneously, be passed in O3 contacted oxidation tower from the water inlet of O3 contacted oxidation tower by waste water simultaneously and react in four dosing mouths of O3 contacted oxidation tower outer wall, and the response time is 45min.
After reaction terminates, collect water outlet from the outlet of O3 contacted oxidation tower, measure the water quality of water outlet.Water outlet CODCrFor 29.7mg/L, colourity is 4 times, and turbidity is 0.26NTU.Waste water after treatment, CODCrClearance be 90.0%, the clearance of colourity is 93.8%, and the clearance of turbidity is 79.9%.
Embodiment 3
Waste water takes from certain reverse osmosis concentrated saline of refinery project of Poten Environment Group Co., Ltd..The initial water quality index of waste water: CODCrFor 289.4mg/L, colourity is 64 times, and turbidity is 1.289NTU.
Taking 1L waste water, measure the pH value of waste water, pH value is 8.8.Adding 0.9g particle diameter in O3 contacted oxidation tower is the ozone oxidation catalyst being loaded with ferrum, cerium, cobalt, copper on the coal-based column-shaped active carbon of 0.4mm, pass into ozone at O3 contacted oxidation tower bottom and carry out continuous aeration, ozone flow is 1.30L/min, dosage is 200mg, in the case, ozone oxidation catalyst presents stable flow regime.260mg sodium hypochlorite is split the quartering, uniformly adds simultaneously, be passed in O3 contacted oxidation tower from the water inlet of O3 contacted oxidation tower by waste water simultaneously and react in four dosing mouths of O3 contacted oxidation tower outer wall, and the response time is 55min.
After reaction terminates, collect water outlet from the outlet of O3 contacted oxidation tower, measure the water quality of water outlet.Water outlet CODCrFor 29.2mg/L, colourity is 4 times, and turbidity is 0.30NTU.Waste water after treatment, CODCrClearance be 89.9%, the clearance of colourity is 93.8%, and the clearance of turbidity is 76.7%.
Embodiment 4
Waste water takes from certain reverse osmosis concentrated saline of thermoelectricity project of Poten Environment Group Co., Ltd..The initial water quality index of waste water: CODCrFor 285.4mg/L, colourity is 64 times, and turbidity is 1.288NTU.
Taking 500ml waste water, measure the pH value of waste water, pH value is 7.4.The ozone oxidation catalyst being loaded with cerium, copper on graininess many silicon clinoptilolite that 0.25g particle diameter is 0.4mm is added in O3 contacted oxidation tower, pass into ozone at O3 contacted oxidation tower bottom and carry out continuous aeration, ozone flow is 1.45L/min, dosage is 160mg, in the case, ozone oxidation catalyst presents stable flow regime.50mg potassium peroxydisulfate is split the quartering, uniformly adds simultaneously, be passed in O3 contacted oxidation tower from the water inlet of O3 contacted oxidation tower by waste water simultaneously and react in four dosing mouths of O3 contacted oxidation tower outer wall, and the response time is 40min.
After reaction terminates, collect water outlet from the outlet of O3 contacted oxidation tower, measure the water quality of water outlet.Water outlet CODCrFor 29.7mg/L, colourity is 4 times, and turbidity is 0.30NTU.Waste water after treatment, CODCrClearance be 89.6%, the clearance of colourity is 93.8%, and the clearance of turbidity is 76.7%.
Embodiment 5
Waste water takes from certain reverse osmosis concentrated saline of thermoelectricity project of Poten Environment Group Co., Ltd..The initial water quality index of waste water: CODCrFor 293.2mg/L, colourity is 64 times, and turbidity is 1.293NTU.
Taking 500ml waste water, measure the pH value of waste water, pH value is 6.7.The ozone oxidation catalyst being loaded with manganese, cerium, cobalt in the particulate molecular sieve that 0.1g particle diameter is 0.3mm is added in O3 contacted oxidation tower, pass into ozone at O3 contacted oxidation tower bottom and carry out continuous aeration, ozone flow is 1.25L/min, dosage is 160mg, in the case, ozone oxidation catalyst presents stable flow regime.40mg potassium peroxydisulfate is split the quartering, uniformly adds simultaneously, be passed in O3 contacted oxidation tower from the water inlet of O3 contacted oxidation tower by waste water simultaneously and react in four dosing mouths of O3 contacted oxidation tower outer wall, and the response time is 30min.
After reaction terminates, collect water outlet from the outlet of O3 contacted oxidation tower, measure the water quality of water outlet.Water outlet CODCrFor 28.5mg/L, colourity is 4 times, and turbidity is 0.29NTU.Waste water after treatment, CODCrClearance be 90.3%, the clearance of colourity is 93.8%, and the clearance of turbidity is 77.6%.
Embodiment 6
Waste water takes from certain reverse osmosis concentrated saline of thermoelectricity project of Poten Environment Group Co., Ltd..The initial water quality index of waste water: CODCrFor 296.8mg/L, colourity is 64 times, and turbidity is 1.289NTU.
Taking 2L waste water, measure the pH value of waste water, pH value is 6.1.Adding 1.2g particle diameter in O3 contacted oxidation tower is the ozone oxidation catalyst being loaded with ferrum, cobalt on the granulated activated aluminium oxide of 0.5mm, pass into ozone at O3 contacted oxidation tower bottom and carry out continuous aeration, ozone flow is 1.15L/min, dosage is 300mg, in the case, ozone oxidation catalyst presents stable flow regime.300mg Ammonium persulfate. is split the quartering, uniformly adds simultaneously, be passed in O3 contacted oxidation tower from the water inlet of O3 contacted oxidation tower by waste water simultaneously and react in four dosing mouths of O3 contacted oxidation tower outer wall, and the response time is 60min.
After reaction terminates, collect water outlet from the outlet of O3 contacted oxidation tower, measure the water quality of water outlet.Water outlet CODCrFor 29.4mg/L, colourity is 4 times, and turbidity is 0.27NTU.Waste water after treatment, CODCrClearance be 90.1%, the clearance of colourity is 93.8%, and the clearance of turbidity is 79.1%.
Embodiment 7
Waste water takes from certain reverse osmosis concentrated saline of thermoelectricity project of Poten Environment Group Co., Ltd..The initial water quality index of waste water: CODCrFor 293.9mg/L, colourity is 64 times, and turbidity is 1.287NTU.
Taking 1L waste water, measure the pH value of waste water, pH value is 11, and pH value is adjusted to 6.The ozone oxidation catalyst being loaded with manganese, ferrum, cobalt in the particulate molecular sieve that 1g particle diameter is 0.3mm is added in O3 contacted oxidation tower, pass into ozone at O3 contacted oxidation tower bottom and carry out continuous aeration, ozone flow is 1.08L/min, dosage is 320mg, in the case, ozone oxidation catalyst presents stable flow regime.120mg sodium peroxydisulfate is split the quartering, four dosing mouths of O3 contacted oxidation tower outer wall uniformly add simultaneously, being passed in O3 contacted oxidation tower from the water inlet of O3 contacted oxidation tower react mixing up the waste water of pH value simultaneously, the response time is 60min.
After reaction terminates, collect water outlet from the outlet of O3 contacted oxidation tower, measure the water quality of water outlet.Water outlet CODCrFor 28.6mg/L, colourity is 4 times, and turbidity is 0.28NTU.Waste water after treatment, CODCrClearance be 90.3%, the clearance of colourity is 93.8%, and the clearance of turbidity is 78.2%.
Comparative example 1
Waste water takes from certain reverse osmosis concentrated saline of refinery project of Poten Environment Group Co., Ltd..The initial water quality index of waste water: CODCrFor 303.7mg/L, colourity is 64 times, and turbidity is 1.285NTU.
Taking 1L waste water, measure the pH value of waste water, pH value is 7.4.The ozone oxidation catalyst being loaded with manganese, nickel, copper in the particulate molecular sieve that 0.3g particle diameter is 0.3mm is added in O3 contacted oxidation tower, pass into ozone at O3 contacted oxidation tower bottom and carry out continuous aeration, ozone flow is 0.30L/min, dosage is 360mg, in the case, ozone oxidation catalyst presents fixing stacking state.100mg hydrogen peroxide is split the quartering, uniformly adds in four dosing mouths of O3 contacted oxidation tower outer wall simultaneously.Being passed in O3 contacted oxidation tower from the water inlet of O3 contacted oxidation tower by waste water and react, the response time is 35min.
After reaction terminates, collect water outlet from the outlet of O3 contacted oxidation tower, measure the water quality of water outlet.Water outlet CODCrFor 82.6mg/L, colourity is 4 times, and turbidity is 0.37NTU.Waste water after treatment, CODCrClearance be 72.8%, the clearance of colourity is 93.8%, and the clearance of turbidity is 71.2%.
Comparative example 2
Waste water takes from certain reverse osmosis concentrated saline of refinery project of Poten Environment Group Co., Ltd..The initial water quality index of waste water: CODCrFor 298.4mg/L, colourity is 64 times, and turbidity is 1.296NTU.
Taking 2L waste water, measure the pH value of waste water, pH value is 6.5.Adding 1g particle diameter in O3 contacted oxidation tower is the ozone oxidation catalyst being loaded with ferrum, nickel, copper on the granular porous pottery of 0.5mm, pass into ozone at O3 contacted oxidation tower bottom and carry out continuous aeration, ozone flow is 1.27L/min, dosage is 474mg, in the case, ozone oxidation catalyst presents stable flow regime.Adding 400mg sodium hypochlorite in O3 contacted oxidation tower water inlet, be passed in O3 contacted oxidation tower from the water inlet of O3 contacted oxidation tower by waste water simultaneously and react, the response time is 45min.
After reaction terminates, collect water outlet from the outlet of O3 contacted oxidation tower, measure the water quality of water outlet.Water outlet CODCrFor 87.1mg/L, colourity is 4 times, and turbidity is 0.40NTU.Waste water after treatment, CODCrClearance be 70.8%, the clearance of colourity is 93.8%, and the clearance of turbidity is 69.1%.
From comparative example 1 and 2 it can be seen that ozone oxidation catalyst and conventional single composite multi-component oxidant dosing mouth with conventional fixing bed do not reach embodiment 1 to 7 and process the effect of waste water.
By above-described embodiment and comparative example it can be seen that the treatment by catalytic oxidation of a kind of reverse osmosis concentrated saline disclosed by the invention, the catalytic efficiency of ozone oxidation catalyst, the COD of reverse osmosis concentrated saline are greatly improvedCrClearance more than 85%, the clearance of colourity is more than 90%, the clearance of turbidity is more than 75%, and after process, water outlet leading indicator all can reach the direct discharge standard that " petro chemical industry pollutant emission standard " (GB31571-2015) specifies.
Above the treatment by catalytic oxidation of a kind of reverse osmosis concentrated saline provided by the present invention is described in detail.Principles of the invention and embodiment are set forth by specific embodiment used herein, and the explanation of above example is only intended to help to understand method and the central idea thereof of the present invention.It should be pointed out that, for the person of ordinary skill of the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify the protection also falling into the claims in the present invention.
Claims (9)
1. the treatment by catalytic oxidation of a reverse osmosis concentrated saline, it is characterised in that comprise the following steps:
Measure the pH value of reverse osmosis concentrated saline；
When the pH value of reverse osmosis concentrated saline is 2～10, reverse osmosis concentrated saline is passed in O3 contacted oxidation tower, composite multi-component oxidant is added in described O3 contacted oxidation tower, described reverse osmosis concentrated saline carries out being fully contacted reaction with the ozone of continuous aeration, fluidization ozone oxidation catalyst and composite multi-component oxidant in described O3 contacted oxidation tower, and the response time is 10～80min；
Described O3 contacted oxidation tower adopts upright type of design, its top is provided with water inlet, bottom is provided with outlet, bottom is provided with ozonation aerated head, for providing the ozone of continuous aeration, it is provided with supporting layer in O3 contacted oxidation tower, described supporting layer is filled with ozone oxidation catalyst, the outer wall of described O3 contacted oxidation tower is provided with the dosing mouth of composite multi-component oxidant；
Specific surface area >=the 300m of described ozone oxidation catalyst2/ g, bulk density is 0.11～0.17g/ml, and dosage is 200～1000mg/L；
Described ozone oxidation catalyst meets fluidised parameter: the particle diameter of described ozone oxidation catalyst is 0.3～0.5mm, comprcssive strength > 160N, wear rate≤0.1%W；
Described ozone dosage is 50～500mg/L；
Described composite multi-component oxidant, including: one or more in persulfate, hydrogen peroxide, calper calcium peroxide, sodium hypochlorite, calcium hypochlorite, chlorine dioxide.
2. treatment by catalytic oxidation according to claim 1, it is characterised in that when the pH value of reverse osmosis concentrated saline is 6～9, reverse osmosis concentrated saline is passed in O3 contacted oxidation tower.
3. treatment by catalytic oxidation according to claim 1, it is characterised in that described ozone oxidation catalyst, including: carrier material and active component；Wherein, described carrier material includes: the one in granular porous aluminium oxide ceramic, granulated activated, particulate molecular sieve, coal-based column-shaped active carbon, graininess active fruit shell carbon, graininess many silicon clinoptilolite；Described active component is one or more in manganese, nickel, ferrum, cerium, cobalt, copper.
4. treatment by catalytic oxidation according to claim 1, it is characterised in that described persulfate includes: one or more in Ammonium persulfate., sodium peroxydisulfate, potassium peroxydisulfate.
5. treatment by catalytic oxidation according to claim 1, it is characterised in that the dosage of described composite multi-component oxidant is 30～300mg/L.
6. treatment by catalytic oxidation according to claim 1, it is characterised in that the mass ratio of described ozone and composite multi-component oxidant is 2:3～5:1.
7. treatment by catalytic oxidation according to claim 1, it is characterised in that the dosing mouth of described composite multi-component oxidant is arranged in described O3 contacted oxidation tower 1/4 place of liquid level, 2/4 place, 3/4 place, 4/4 place.
8. treatment by catalytic oxidation according to claim 7, it is characterised in that described composite multi-component oxidant uniformly adds at four dosing mouths simultaneously.
9. treatment by catalytic oxidation according to claim 1, it is characterised in that described O3 contacted oxidation tower also includes internal circulation apparatus；
Described treatment by catalytic oxidation also includes: starting circulating pump, the reverse osmosis concentrated saline in described O3 contacted oxidation tower is circulated process, described quantity of circulating water is the 10%～50% of inflow.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345485A (en) * | 2016-08-25 | 2017-01-25 | 万华化学集团股份有限公司 | Catalyst for catalytic oxidation treatment of organic waste water, and preparation method and purpose thereof |
| CN106587470A (en) * | 2016-11-23 | 2017-04-26 | 山东东岳氟硅材料有限公司 | Method and process system for innocuous treatment of high-salt and high-COD waste alkali liquid |
| CN106630266A (en) * | 2016-11-30 | 2017-05-10 | 青岛双瑞海洋环境工程股份有限公司 | Domestic sewage treatment method and equipment |
| WO2018035883A1 (en) * | 2016-08-25 | 2018-03-01 | 万华化学集团股份有限公司 | Method for treating reverse osmosis concentrated water |
| CN109081422A (en) * | 2018-08-27 | 2018-12-25 | 南京泽辉环保科技有限公司 | A method of utilizing low-concentration ammonia-nitrogen in ozone and micro calper calcium peroxide removal water body |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007083171A (en) * | 2005-09-22 | 2007-04-05 | Fuji Electric Systems Co Ltd | Method and apparatus for treating water |
| CN101327985A (en) * | 2008-07-31 | 2008-12-24 | 哈尔滨工业大学 | Method for removing organic pollutant in water by catalysis ozonation |
| CN101385971A (en) * | 2007-09-13 | 2009-03-18 | 中国科学院生态环境研究中心 | Catalyst preparation method for efficiently catalyzing organic pollutant in ozone oxidation water |
| CN102126781A (en) * | 2011-04-20 | 2011-07-20 | 中国石油天然气集团公司 | Method for treating reverse osmosis concentrates of petrochemical wastewater |
| CN102489251A (en) * | 2011-12-08 | 2012-06-13 | 哈尔滨工业大学 | Multifunctional up-flow granular active carbon adsorption bed and method thereof for removing organic pollutants in water |
| CN102580759A (en) * | 2011-01-18 | 2012-07-18 | 中国科学院生态环境研究中心 | Water purification method capable of realizing in-situ preparation and in-situ regeneration of catalyst and catalyzing zone to oxidize organic micropollutants |
| CN103058346A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Wastewater treatment method |
| CN204058048U (en) * | 2014-08-12 | 2014-12-31 | 苏州科技学院 | For the device of heterogeneous catalysis ozone Oxidation Treatment water |
| CN204265513U (en) * | 2014-09-29 | 2015-04-15 | 博天环境集团股份有限公司 | Heterocatalysis ozone-oxidizing device |
| CN104529001A (en) * | 2014-12-24 | 2015-04-22 | 北京桑德环境工程有限公司 | Catalytic ozonation fluidized bed reactor for efficiently removing CODcr in wastewater |
| CN104556347A (en) * | 2014-12-15 | 2015-04-29 | 浙江中凯瑞普环境工程股份有限公司 | Wastewater treatment catalytic ozonation reactor for fluidized bed and wastewater treatment method of wastewater treatment catalytic ozonation reactor |
-
2016
- 2016-02-19 CN CN201610094307.1A patent/CN105731629A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007083171A (en) * | 2005-09-22 | 2007-04-05 | Fuji Electric Systems Co Ltd | Method and apparatus for treating water |
| CN101385971A (en) * | 2007-09-13 | 2009-03-18 | 中国科学院生态环境研究中心 | Catalyst preparation method for efficiently catalyzing organic pollutant in ozone oxidation water |
| CN101327985A (en) * | 2008-07-31 | 2008-12-24 | 哈尔滨工业大学 | Method for removing organic pollutant in water by catalysis ozonation |
| CN102580759A (en) * | 2011-01-18 | 2012-07-18 | 中国科学院生态环境研究中心 | Water purification method capable of realizing in-situ preparation and in-situ regeneration of catalyst and catalyzing zone to oxidize organic micropollutants |
| CN102126781A (en) * | 2011-04-20 | 2011-07-20 | 中国石油天然气集团公司 | Method for treating reverse osmosis concentrates of petrochemical wastewater |
| CN103058346A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Wastewater treatment method |
| CN102489251A (en) * | 2011-12-08 | 2012-06-13 | 哈尔滨工业大学 | Multifunctional up-flow granular active carbon adsorption bed and method thereof for removing organic pollutants in water |
| CN204058048U (en) * | 2014-08-12 | 2014-12-31 | 苏州科技学院 | For the device of heterogeneous catalysis ozone Oxidation Treatment water |
| CN204265513U (en) * | 2014-09-29 | 2015-04-15 | 博天环境集团股份有限公司 | Heterocatalysis ozone-oxidizing device |
| CN104556347A (en) * | 2014-12-15 | 2015-04-29 | 浙江中凯瑞普环境工程股份有限公司 | Wastewater treatment catalytic ozonation reactor for fluidized bed and wastewater treatment method of wastewater treatment catalytic ozonation reactor |
| CN104529001A (en) * | 2014-12-24 | 2015-04-22 | 北京桑德环境工程有限公司 | Catalytic ozonation fluidized bed reactor for efficiently removing CODcr in wastewater |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345485A (en) * | 2016-08-25 | 2017-01-25 | 万华化学集团股份有限公司 | Catalyst for catalytic oxidation treatment of organic waste water, and preparation method and purpose thereof |
| WO2018035882A1 (en) * | 2016-08-25 | 2018-03-01 | 万华化学集团股份有限公司 | Catalyst for catalytic oxidation treatment of organic wastewater, preparation method therefor, and application thereof |
| WO2018035883A1 (en) * | 2016-08-25 | 2018-03-01 | 万华化学集团股份有限公司 | Method for treating reverse osmosis concentrated water |
| CN106345485B (en) * | 2016-08-25 | 2018-12-07 | 万华化学集团股份有限公司 | A kind of catalyst and its preparation method and application for catalytic oxidation treatment organic wastewater |
| US10696574B2 (en) | 2016-08-25 | 2020-06-30 | Wanhua Chemical Group Co., Ltd. | Method for treating reverse osmosis concentrated water |
| US11059033B2 (en) | 2016-08-25 | 2021-07-13 | Wanhua Chemical Group Co., Ltd. | Catalyst for catalytic oxidation treatment of organic wastewater, preparation method thereof, and application thereof |
| CN106587470A (en) * | 2016-11-23 | 2017-04-26 | 山东东岳氟硅材料有限公司 | Method and process system for innocuous treatment of high-salt and high-COD waste alkali liquid |
| CN106630266A (en) * | 2016-11-30 | 2017-05-10 | 青岛双瑞海洋环境工程股份有限公司 | Domestic sewage treatment method and equipment |
| CN109081422A (en) * | 2018-08-27 | 2018-12-25 | 南京泽辉环保科技有限公司 | A method of utilizing low-concentration ammonia-nitrogen in ozone and micro calper calcium peroxide removal water body |
| CN109081422B (en) * | 2018-08-27 | 2022-03-04 | 南京泽辉环保科技有限公司 | Method for removing low-concentration ammonia nitrogen in water body by using ozone and trace calcium peroxide |
| CN113735302A (en) * | 2020-05-28 | 2021-12-03 | 宝山钢铁股份有限公司 | Method and device for removing SCOD (selective catalytic reduction) and total nitrogen in cold-rolling biochemical effluent |
| CN112358028A (en) * | 2020-11-01 | 2021-02-12 | 广东蓝绿科技有限公司 | Wastewater treatment process based on ozone |
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