CN105753133B - A kind of catalytic ozonation tower and the method using its gas treatment waste water - Google Patents

A kind of catalytic ozonation tower and the method using its gas treatment waste water Download PDF

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CN105753133B
CN105753133B CN201610095107.8A CN201610095107A CN105753133B CN 105753133 B CN105753133 B CN 105753133B CN 201610095107 A CN201610095107 A CN 201610095107A CN 105753133 B CN105753133 B CN 105753133B
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aeration disc
microporous aeration
ozone
tower
oxidation catalyst
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CN105753133A (en
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乔瑞平
耿翠玉
蒋玮
陈广升
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Poten Environment Group Co Ltd
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Poten Environment Group Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The embodiment of the invention discloses a kind of catalytic ozonation towers, including oxidizing tower ontology, ozone generator, circulating pump and tail gas breaking plant；Oxidizing tower ontology includes the first microporous aeration disc, the second microporous aeration disc, catalyst layer, water inlet, water outlet, at least one oxidant dosing mouth, exhaust outlet, circulation water inlet and circulating outlet；First microporous aeration disc is located at oxidizing tower body bottom portion；Second microporous aeration disc is located above the first microporous aeration disc；Catalyst layer is located above the second microporous aeration disc；It is disposed with water inlet and circulation water inlet from the bottom to top on oxidizing tower this body sidewall between the first microporous aeration disc and the second microporous aeration disc；It is disposed with circulating outlet and water outlet from the bottom to top on tower body side wall above catalyst layer；At least one oxidant dosing mouth is provided on oxidizing tower this body sidewall between water inlet and circulating outlet.The oxidizing tower can shorten residence time of the ozone in tower, improve ozone utilization rate.

Description

A kind of catalytic ozonation tower and the method using its gas treatment waste water
Technical field
The present invention relates to field of industrial waste water treatment, in particular to a kind of catalytic ozonation tower and apply its gas treatment Change the method for waste water.
Background technique
The water-quality constituents of coal gasification waste water is complicated, wherein having containing a large amount of phenols, biphenyl, pyridine, indoles and quinoline etc. Machine pollutant, also containing poisonous and harmful substances such as cyanogen, inorganic fluorion and ammonia nitrogens, pollutant concentration is high, and coloration is also high, and it is more difficult to belong to The high-concentration organic industrial waste water of biochemical degradation.Therefore the processing of coal gasification waste water, is always domestic and international field of waste water treatment A great problem.
In order to solve above-mentioned problem, China application No. is 201110045621.8 application for a patent for invention disclose it is a kind of smelly The process of oxygen catalytic oxidation treatment oil refining wastewater reverse osmosis concentrated water uses catalytic ozonation work under normal temperature and pressure conditions Skill handles oil refining wastewater reverse osmosis concentrated water.Concrete technology flow process is reverse osmosis concentrated water after conditioning tank homogeneous, through supplying Water pump enters pre-exposure gas tank, and water, which is sufficiently mixed in tank with the ozone provided by ozone generator, to react, be discharged it is boosted pump into Enter catalytic oxidation tower, is discharged up to the primary standard in comprehensive discharge standard (GB8978-1996).Pre-exposure gas tank and catalysis The tail gas of oxidation reaction tower discharge enters exhaust purifier, purified gas discharge.Oxygen of this method for organic pollutant Change processing to need that first oil refining wastewater reverse osmosis concentrated water is sent into pre-exposure gas tank through ozone Oxidation Treatment, is re-fed into catalysis oxidizing tower In further utilize catalyst carry out oxidation processes.It can be seen that not giving full play to ozone in pre-exposure gas tank for organic The oxidation of pollutant, it is also necessary to oil refining wastewater reverse osmosis concentrated water is re-fed into catalysis oxidizing tower and further utilize catalyst Carry out oxidation processes.The extracting that such oxidation processes need to pump twice, process show slightly cumbersome, and need two kinds of devices (pre-exposure gas tank and catalysis oxidizing tower) takes up a large area in the reverse osmosis concentrated Hydraulic Projects of actual treatment oil refining wastewater, invests and transport Row is at high cost.
Summary of the invention
The embodiment of the invention discloses a kind of catalytic ozonation towers, for solving coal gasification waste water in oxidation processes It is middle to need multiple reaction units, lead to cumbersome process, investment and the high problem of operating cost.Technical solution is as follows:
A kind of catalytic ozonation tower, the oxidizing tower include that oxidizing tower ontology, ozone generator, circulating pump and tail gas destroy Device；
The oxidizing tower ontology includes the first microporous aeration disc, the second microporous aeration disc, catalyst layer, water inlet, water outlet Mouth, at least one oxidant dosing mouth, exhaust outlet, circulation water inlet and circulating outlet；
First microporous aeration disc is located at oxidizing tower body bottom portion；Second microporous aeration disc is located on the first microporous aeration disc Side；Catalyst layer is located above the second microporous aeration disc；First microporous aeration disc and the second microporous aeration disc pass through pipeline respectively It is connected with ozone generator；
It is successively set from the bottom to top on oxidizing tower this body sidewall between the first microporous aeration disc and the second microporous aeration disc It is equipped with water inlet and circulation water inlet；It is disposed with circulating outlet from the bottom to top on tower body side wall above catalyst layer And water outlet；At least one oxidant dosing is provided on oxidizing tower this body sidewall between water inlet and circulating outlet Mouthful；Oxidizing tower bodies top is provided with exhaust outlet, exhaust outlet is connected by pipeline with tail gas breaking plant；Circulating pump into Water end (W.E.) is connected by pipeline with circulating outlet, and the water outlet of circulating pump is connected by pipeline with circulation water inlet.
In the preferred embodiment of the present invention, second microporous aeration disc is located at the first microporous aeration disc to out At the 1/2 of mouth of a river height.
In the preferred embodiment of the present invention, oxidizing tower this body sidewall between water inlet and circulating outlet On be provided with 2 oxidant dosing mouths, preferably 4 oxidant dosing mouths.
The invention also discloses a kind of methods of gas treatment waste water, comprising the following steps:
The pH value of coal gasification waste water is adjusted to 4~10, preferably 6~9, carries out coagulating kinetics later, it will be through coagulation After the pH value for the supernatant that precipitation process obtains is adjusted to 7~9, it is transported to progress ozone in above-mentioned catalytic ozonation tower and urges Change oxidation processes, and adds oxidant into catalytic ozonation tower；Circulation in carrying out simultaneously；Supernatant is in catalytic ozonation Residence time in tower is 10~60 minutes；Catalyst in catalytic ozonation tower is the catalysis of Poten-SOT type ozone oxidation Agent；The dosage of ozone and oxidant in the supernatant in the oxidizing tower is respectively 50~350mg/L and 50~300mg/ L；
The Poten-SOT type ozone oxidation catalyst is made by following steps:
Ozone oxidation catalyst carrier is pre-processed；The pretreatment is first to carry out ozone oxidation catalyst carrier It washes at least once, then is immersed in 1~48h in acid solution, be washed out to neutrality, be finally dried；
Pretreated ozone oxidation catalyst carrier is subjected to impregnation at least once, the impregnation is will be pre- Treated, and ozone oxidation catalyst carrier is immersed in dipping solution, and 20~100 DEG C of 6~48h of immersion are dried later； The dipping solution be the nitrate containing metallic elements at least three kinds of in manganese, nickel, iron, cerium, cobalt and copper, sulfate, acetate or The mixed solution of chloride；Concentration of at least three kinds of metallic elements in dipping solution is respectively 0.01~1.00mol/L；
Ozone oxidation catalyst carrier after dipping is subjected to calcination process.
In the preferred embodiment of the present invention, the ozone oxidation catalyst carrier is selected from granular porous pottery Porcelain, granulated activated aluminium oxide, particulate molecular sieve, coal pilum shaped activated carbon, graininess active fruit shell carbon or the more silicon of graininess Clinoptilolite, and its partial size is 3~6mm, specific surface area >=250m2/ g, compression strength > 100N, bulk density > 0.17g/ mL。
In a kind of more preferable embodiment of the invention, the dipping solution is 6 kinds in manganese, nickel, iron, cerium, cobalt and copper The nitrate of metallic element, sulfate, acetate or chloride mixed solution, wherein manganese, nickel, iron, cerium, cobalt and copper The ratio between the amount of substance be (1~50): (1~50): (1~50): (1~50): (1~30): (1~30), and manganese, nickel, iron, The concentration of cerium, cobalt and copper in dipping solution is respectively 0.01~0.50mol/L.
In the preferred embodiment of the present invention, it is described pretreatment for first by ozone oxidation catalyst carrier carry out to Few primary washing, then be immersed in the nitric acid solution of 0.01~1.00mol/L 10~30 hours, it is preferable that 0.05~ 10~24 hours in the nitric acid solution of 0.15mol/L, it is washed out to neutrality, is finally dried.
In the preferred embodiment of the present invention, the coagulating kinetics are that nothing is first added into coagulative precipitation tank Machine coagulant is stirred 0.5~3.0 minute with 100~300 revs/min of revolving speed, then organic-flocculation is added into coagulative precipitation tank Agent is stirred 0.5~3.0 minute with 100~300 revs/min of revolving speed, adjusts revolving speed later to 30~100 revs/min, and stirring 10~ 30 minutes, last quiescent setting.
In a kind of more preferable embodiment of the invention, the inorganic coagulant be aluminium polychloride, bodied ferric sulfate, At least one of polyaluminum ferric chloride, polyaluminium sulfate, aluminum sulfate；The organic flocculant be cationic polyacrylamide, At least one of anionic polyacrylamide, polyacrylamide of partial hydrolysis；The inorganic coagulant and organic wadding Solidifying dosage of the agent in the coal gasification waste water for mixing up pH value is respectively 100~1000mg/L and 1~30mg/L；Oxidant was At least one of hydrogen oxide, sodium hypochlorite, chlorine dioxide and chlorine.
In the preferred embodiment of the present invention, the reflux ratio of the interior circulation is 3:5~6:5.
The embodiment of the invention discloses a kind of catalytic ozonation towers, only need a catalytic ozonation tower that coal can be completed The oxidation processes of gasification waste water so that oxidation processes are easy to operate, and reduce investment and operating cost.Together When, which is shortened residence time of the ozone in tower, is improved the utilization of ozone using the structure design being aerated twice Rate.In addition, graded oxidation reaction is carried out to the pollutant in waste water, first under ozone and oxidant effect, by easy degradation Pollutant removal falls, then under ozone, ozone oxidation catalyst and oxidant three's collective effect, and stability is high, difficult to degrade Pollutant removal fall, to reduce catalyst amount, reduce the operating cost of wastewater treatment.The embodiment of the present invention is also public The method using the oxidizing tower gas treatment waste water has been opened, simple process can effectively remove the pollutant in coal gasification waste water, Effluent index is much higher than " integrated wastewater discharge standard " (GB 8978-1996) first discharge standard.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with It obtains other drawings based on these drawings.
Fig. 1 is a kind of structural schematic diagram of catalytic ozonation tower provided in an embodiment of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Referring to Fig. 1, technical solution of the present invention: a kind of gradient catalytic ozonation tower, the oxidizing tower are included at least: oxidizing tower Ontology 100, ozone generator 200, circulating pump 300 and tail gas breaking plant 400；Oxidizing tower ontology 100 is exposed including the first micropore Gas disk 101, the second microporous aeration disc 102, catalyst layer 103, water inlet 104, water outlet 105, at least one oxidant dosing Mouth 106, exhaust outlet 107, circulation water inlet 109 and circulating outlet 108；First microporous aeration disc 101 is located at oxidizing tower ontology 100 bottoms；Second microporous aeration disc 102 is located at 101 top of the first microporous aeration disc；Catalyst layer 103 is located at the exposure of the second micropore 102 top of gas disk；First microporous aeration disc 101 and the second microporous aeration disc 102 pass through pipeline and 200 phase of ozone generator respectively Connection；On oxidizing tower this body sidewall between the first microporous aeration disc 101 and the second microporous aeration disc 102 from the bottom to top successively It is provided with water inlet 104 and circulation water inlet 109；On oxidizing tower this body sidewall above catalyst layer 103 from the bottom to top according to It is secondary to be provided with circulating outlet 108 and water outlet 105；This side of oxidizing tower between water inlet 104 and circulating outlet 108 At least one oxidant dosing mouth 106 is provided on wall；Oxidizing tower bodies top is provided with exhaust outlet 107, exhaust outlet 107 is logical Pipeline is crossed to be connected with tail gas breaking plant 400；The water inlet end of circulating pump 300 is connected by pipeline with circulating outlet 108, The water outlet of circulating pump 300 is connected by pipeline with circulation water inlet 109.
In practical applications, on the pipeline that the first microporous aeration disc and the second microporous aeration disc are connect with ozone generator It is respectively arranged with gas flowmeter, the ozone amount of ozone generator generation can be adjusted according to the COD (COD) of waste water And the ozone amount that two microporous aeration discs expose, the aeration quantity of usual first microporous aeration disc and the aeration of the second microporous aeration disc The ratio between amount can be 1:3~3:1.
In the inventive solutions, it is preferable that the second microporous aeration disc 102 is located at the first microporous aeration disc 101 and arrives At the 1/2 of 105 height of water outlet.This structure designs so that oxidizing tower is divided into two reaction zones by the second microporous aeration disc, under Side is oxidation reaction zone, and top is catalytic oxidation area.In zoneofoxidation, ozone and oxidant collective effect handle waste water；? Catalytic oxidation area, ozone, ozone oxidation catalyst and oxidant collective effect handle waste water, not only shorten ozone in oxygen Change the residence time in tower, and reduce the dosage of ozone catalyst, to save the operating cost of wastewater treatment.
In the inventive solutions, on oxidizing tower this body sidewall between water inlet 104 and circulating outlet 108 2 oxidant dosing mouths 106, preferably 4 oxidant dosing mouths 106 are provided with, and oxidant dosing mouth is in oxidizing tower sheet It is distributed vertically on body sidewall.Be conducive to oxidant quickly fully to contact with the realization of waste water, ozone and ozone oxidation catalyst, keep away Exempt to influence treatment effect to waste water because oxidant local concentration is too high or too low.
Explanation is needed further exist for, above-mentioned each improved technical solution both can individually be implemented, and can also combine It comes together to implement, which kind of embodiment is specifically used, can be determined by those skilled in the art according to actual treatment situation, this Invention is not specifically limited herein.
When above-mentioned each improved solution pool together when, can be as shown in Figure 1, the oxidizing tower includes: oxidizing tower Ontology 100, ozone generator 200, circulating pump 300 and tail gas breaking plant 400；Oxidizing tower ontology 100 is exposed including the first micropore Gas disk 101, the second microporous aeration disc 102, catalyst layer 103, water inlet 104,105,4 oxidant dosing mouths 106 of water outlet, Exhaust outlet 107, circulation water inlet 109 and circulating outlet 108；First microporous aeration disc 101 is located at 100 bottom of oxidizing tower ontology Portion；Second microporous aeration disc 102 is located at the first microporous aeration disc 101 at the 1/2 of 105 height of water outlet；Catalyst layer 103 Above the second microporous aeration disc 102；First microporous aeration disc 101 and the second microporous aeration disc 102 respectively by pipeline with it is smelly Oxygen Generator 200 is connected；Oxidizing tower this body sidewall between the first microporous aeration disc 101 and the second microporous aeration disc 102 On be disposed with water inlet 104 and circulation water inlet 109 from the bottom to top；This side of oxidizing tower above catalyst layer 103 Circulating outlet 108 and water outlet 105 are disposed on wall from the bottom to top；Between water inlet 104 and circulating outlet 108 Oxidizing tower this body sidewall on be provided with 4 oxidant dosing mouths 106；Oxidizing tower bodies top is provided with exhaust outlet 107, arranges Port 107 is connected by pipeline with tail gas breaking plant 400；The water inlet end of circulating pump 300 passes through pipeline and circulating outlet 108 are connected, and the water outlet of circulating pump 300 is connected by pipeline with circulation water inlet 109.
The process flow of catalytic ozonation tower provided by the invention are as follows: the ozone point that ozone generator device 200 generates For two parts, a part enters the first microporous aeration disc 101 by the road, and another part is upper by the road to enter the second microporous aeration disc 102.Waste water to be processed is entered inside oxidizing tower ontology 100 by water inlet 104, successively passes through 101 institute of the first microporous aeration disc Ozone oxidation reaction area and the second microporous aeration disc 102 where catalytic ozonation reaction zone, simultaneous oxidation agent, such as mistake Hydrogen oxide is added from 4 oxidant dosing mouths 106 respectively, and waste water first passes through ozone and is jointly processed by with oxidant, degradable Organic matter be first oxidized and decompose, be jointly processed by using ozone, ozone oxidation catalyst and oxidant three, wherein difficult drop The organic matter of solution is degraded to small molecule organic compound or carbon dioxide and water, and processed waste water is discharged through water outlet 105；It is remaining Ozone in oxidizing tower collected overhead, got rid of from exhaust outlet 107 into tail gas breaking plant 400.Meanwhile in order to further increase Adding ozone utilization rate and oxidation efficiency, the waste water in oxidizing tower ontology 100 enters in circulating pump 300 from circulating outlet 108, then In from circulation water inlet 109 back to oxidizing tower ontology 100, homogeneous mixing and repeated multiple times processing are carried out to waste water.
The invention also discloses a kind of methods of gas treatment waste water, comprising the following steps: by the pH of coal gasification waste water Value is adjusted to 4~10, preferably 6~9, carries out coagulating kinetics later, by the pH of the supernatant obtained through coagulating kinetics It after value is adjusted to 7~9, is transported in above-mentioned catalytic ozonation tower and carries out catalytic ozonation processing, and to ozone catalytic Oxidant is added in oxidizing tower；Circulation in carrying out simultaneously；Residence time of the supernatant in catalytic ozonation tower is 10~60 Minute；Catalyst in catalytic ozonation tower is Poten-SOT type ozone oxidation catalyst；Ozone and oxidant are in the oxygen The dosage changed in the supernatant in tower is respectively 50~350mg/L and 50~300mg/L；
Poten-SOT type ozone oxidation catalyst is made by following steps: ozone oxidation catalyst carrier is carried out in advance Reason；The pretreatment for first ozone oxidation catalyst carrier is washed at least once, then be immersed in 1 in acid solution~ 48h is washed out to neutrality, is finally dried；Pretreated ozone oxidation catalyst carrier is soaked at least once Stain processing, the impregnation are that pretreated ozone oxidation catalyst carrier is immersed in dipping solution, 20~100 DEG C 6~48h is impregnated, is dried later；The dipping solution is to contain at least three kinds of metallic elements in manganese, nickel, iron, cerium, cobalt and copper Nitrate, sulfate, acetate or chloride mixed solution；At least three kinds of metallic elements are dense in dipping solution Degree is respectively 0.01~1.00mol/L；Ozone oxidation catalyst carrier after dipping is subjected to calcination process.
The method of gas treatment waste water disclosed by the invention is first reduced at subsequent ozone oxidation using coagulating kinetics The load of reason process utilizes Poten Environment Group Co., Ltd.'s independent research during ozone Oxidation Treatment Poten-SOT type ozone oxidation catalyst strengthens catalytic ozonation effect.The process is easy to operate, in practical application In, occupied area is small, is suitble to apply in much creating or proposing mark transformation project.
It should be noted that the pH value of coal gasification waste water is adjusted to 4~10, preferably 6~9, more conducively coagulating sedimentation mistake Cheng Zhong, the sedimentation of larger molecular organics in waste water, the supernatant after precipitating, which is sent into catalytic ozonation tower, carries out ozone catalytic Oxidation processes, waste water elder generation and oxidant and ozone reaction, wherein the pollutant for being easy degradation is first degraded, on the water surface It rises, waste water is contacted with Poten-SOT type ozone oxidation catalyst again, and under the effect of the catalyst, ozone decomposition produces more Hydroxyl radical free radical (xOH), hydroxyl radical free radical have extremely strong oxidability, non-selectivity quickly oxygenolysis even mineralising Most high stabilities in waste water, pollutant difficult to degrade.In actual waste water treatment process, due to different process source Coal gasification waste water water quality difference it is bigger, therefore, can be useless to coal gasification first before the pH value for adjusting coal gasification waste water Water carries out homogenization, to mitigate the impact load to subsequent processing.The pH value adjusting of waste water is this field conventional means, used The acid-base modifier arrived, those skilled in the art can select according to the actual situation, and the present invention is not specifically limited herein, such as acid Class regulator can be at least one of sulfuric acid, nitric acid, acetic acid, citric acid, and bases regulator can be sodium hydroxide, hydrogen-oxygen Change at least one of calcium, calcium oxide, magnesia, sodium carbonate, quick lime.
It is this field preparation for pretreatment and calcination process in the preparation method of Poten-SOT type ozone oxidation catalyst The conventional means of catalyst, those skilled in the art can voluntarily select the condition of pretreatment and calcination process according to the actual situation, The present invention is not specifically limited herein.Pretreatment can for first ozone oxidation catalyst carrier is washed at least once, then It is immersed in 1~48h in acid solution, is washed out to neutrality, is finally dried, preferably first by ozone oxidation catalyst Carrier is washed at least once, then is immersed in the nitric acid solution of 0.01~1.00mol/L 10~30 hours, preferably Ground 10~24 hours in the nitric acid solution of 0.05~0.15mol/L, is washed out to neutrality, is dried.The temperature of drying process Degree and time, those skilled in the art can also voluntarily select, and can be 60~90 DEG C of dry 10~48h.For calcination process Temperature and time can be 400~500 DEG C of 2~4h of roasting.The present invention uses the impregnation of ozone oxidation catalyst carrier Impregnation at least once, preferably 2~5 this impregnation, so that table of the active component of ozone oxidation catalyst in carrier There are load in layer and inside, and load securely, can efficiently reduce the dissolution of active component.
It should be further noted that the method for gas treatment waste water disclosed by the invention, the preferably chemistry in waste water The concentration of oxygen demand is no more than 1000mg/L.
In the inventive solutions, ozone oxidation catalyst carrier is selected from granular porous ceramic, granulated activated Aluminium oxide, particulate molecular sieve, coal pilum shaped activated carbon, graininess active fruit shell carbon or the more silicon clinoptilolites of graininess, and Its partial size is 3~6mm, specific surface area >=250m2/ g, compression strength > 100N, bulk density > 0.17g/mL.Under this parameter The ozone oxidation catalyst that carrier is prepared not only excellent catalytic effect, and easily presentation fluidization when treating wastewater, and be not easy It is damaged.
In the inventive solutions, dipping solution is the nitric acid of 6 kinds of metallic elements in manganese, nickel, iron, cerium, cobalt and copper Salt, sulfate, acetate or chloride mixed solution, wherein the ratio between manganese, nickel, iron, cerium, cobalt and amount of substance of copper For (1~50): (1~50): (1~50): (1~50): (1~30): (1~30), and manganese, nickel, iron, cerium, cobalt and copper Concentration in dipping solution is respectively 0.01~0.50mol/L.Active component under this parameter is in ozone oxidation catalyst Load capacity is moderate, can be realized higher catalytic activity, while efficient and rational can also utilize dipping solution.
In the inventive solutions, those skilled in the art can carry out coagulating kinetics based on practical experience, excellent It is selected as that inorganic coagulant is first added into coagulative precipitation tank, is stirred 0.5~3.0 minute with 100~300 revs/min of revolving speed, then to Organic flocculant is added in coagulative precipitation tank, is stirred 0.5~3.0 minute with 100~300 revs/min of revolving speed, adjusts revolving speed later To 30~100 revs/min, stir 10~30 minutes, last quiescent setting.Inorganic coagulant and organic flocculant, it is especially organic Flocculant can generate bonding bridging action with most of pollutant in waste water, form the very big reticular structure of surface area, make dirt Dye object is separated from waste water and is settled, and the revolving speed of stirring gradually slows down, and is in order not to destroy established reticular structure, with advantageous The sedimentation of larger molecular organics substance in waste water, under above-mentioned stirring rate and mixing time, larger molecular organics in waste water The effect of settling of matter is more preferably.
It should be noted that those skilled in the art can select inorganic coagulant and organic flocculant based on practical experience Type and dosage are added with oxidant, it is preferable that inorganic coagulant is aluminium polychloride (PAC), bodied ferric sulfate (PFS), at least one of polyaluminum ferric chloride (PAFC), polyaluminium sulfate (PAS), aluminum sulfate (AS)；Organic flocculant is Cationic polyacrylamide (CPAM), anionic polyacrylamide (APAM), partial hydrolysis polyacrylamide (HPAM) in It is at least one；The dosage of inorganic coagulant and organic flocculant in the coal gasification waste water for mixing up pH value is respectively 100~ 1000mg/L and 1~30mg/L；Oxidant is at least one of hydrogen peroxide, sodium hypochlorite, chlorine dioxide and chlorine；.
It should be noted that in catalytic ozonation treatment process, in order to reach the waste water in catalytic ozonation tower out Water index, it usually needs circulation in carrying out is mixed with realizing that waste water comes into full contact with oxidant, ozone and ozone oxidation catalyst Waste water is handled repeatedly.Those skilled in the art can determine the interior reflux ratio recycled according to the water quality of waste water.In skill of the invention In art scheme, it is preferable that the reflux ratio of interior circulation is 3:5~6:5.
Technical solution of the present invention is described below in conjunction with specific embodiment, described embodiment is only this Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
Reagent used in embodiment is commercially available.
(1), the preparation of Poten-SOT type ozone oxidation catalyst
Embodiment 1
Support pre-treatment step selects coal pilum shaped activated carbon (diameter 6mm, specific surface area >=800m2/ g, compression strength > 96N, bulk density > 0.45g/ml) it is ozone oxidation catalyst carrier material, it is cleaned 5 times with clear water, then in 0.03mol/L Dust technology immersion treatment 40h, it is neutral for finally being washed again with clear water to supernatant pH, and it is standby that 48h is baked in 60 DEG C of baking oven With；
Impregnation step, preparing final concentration is respectively 0.60mol/L manganese nitrate, 0.02mol/L nickel nitrate, 0.02mol/ L ferric nitrate, 0.05mol/L cerium chloride, 0.08mol/L copper acetate mixing salt solution, pretreated ozone oxidation is catalyzed Agent carrier material is put into above-mentioned mixing salt solution according to the dosage of 140g/L, concussion dipping 8h, leaching in 80 DEG C of water-bath Dipping object is filtered out after the completion of stain, the dry 28h in 78 DEG C of baking oven is repeated above-mentioned dip operation 2 times, spare；
Calcination process step, the Muffle kiln roasting 4h for being 480 DEG C in maturing temperature by the solid particle after multiple dipping, Obtain Poten-SOT type ozone oxidation catalyst.
Embodiment 2
Support pre-treatment step selects porous ceramics bead (partial size 5mm, specific surface area >=240m2/ g, compression strength > 140N, bulk density > 0.17g/ml) it is ozone oxidation catalyst carrier material, it is cleaned 2 times with clear water, then in 0.08mol/ For 24 hours, it is neutral for finally being washed again with clear water to supernatant pH to the dust technology immersion treatment of L, is baked in 90 DEG C of baking oven standby for 24 hours With；
Impregnation step prepares manganese nitrate, nickel nitrate, ferric nitrate, cerous nitrate, nitre that final concentration is 0.10mol/L The mixing salt solution of sour cobalt, copper nitrate, by pretreated ozone oxidation catalyst carrier material according to the dosage of 150g/L It puts into above-mentioned mixing salt solution, concussion dipping for 24 hours, filters out dipping object after the completion of dipping, at 90 DEG C in 80 DEG C of water-bath It is dry in baking oven to repeat above-mentioned dip operation 2 times for 24 hours, it is spare；
Calcination process step, the Muffle kiln roasting 6h for being 400 DEG C in maturing temperature by the solid particle after multiple dipping, Obtain Poten-SOT type ozone oxidation catalyst.
Embodiment 3
Support pre-treatment step selects molecular sieve (model ZSM-5, partial size 6mm, specific surface area >=350m2/ g resists Compressive Strength > 120N, SiO2/Al2O3It is 25~400, bulk density > 0.75g/ml) it is ozone oxidation catalyst carrier material, It is cleaned 4 times with clear water, then in the dust technology immersion treatment 28h of 0.04mol/L, is finally washed again with clear water to supernatant pH and be Property, it is spare that 45h is baked in 65 DEG C of baking oven；
Impregnation step, prepare final concentration be respectively the manganese nitrate of 0.02mol/L, 0.60mol/L nickel sulfate, The iron chloride of 0.60mol/L, the cerous sulfate of 0.60mol/L, 0.40mol/L cobalt chloride, the mixing of 0.40mol/L copper chloride are molten Liquid puts into pretreated ozone oxidation catalyst carrier material in above-mentioned mixing salt solution according to the dosage of 40g/L, Concussion dipping 30h in 85 DEG C of water-bath, dipping is after the completion with dipping object is filtered out, and drying for 24 hours, repeats above-mentioned in 80 DEG C of baking oven It is dip operation 4 times, spare；
Calcination process step, the Muffle kiln roasting 6h for being 550 DEG C in maturing temperature by the solid particle after multiple dipping, Obtain Poten-SOT type ozone oxidation catalyst.
Embodiment 4
Support pre-treatment step selects more silicon clinoptilolites (partial size 5mm, specific surface area >=500m2/ g, bulk density > 0.45g/ml, wear rate≤0.5%W) it is ozone oxidation catalyst carrier material, it is cleaned 2 times with clear water, then in 0.03mol/ The dust technology immersion treatment 48h of L, it is neutral for finally being washed again with clear water to supernatant pH, and it is standby that 30h is baked in 85 DEG C of baking oven With；
Impregnation step, compound concentration be respectively the manganese nitrate of 0.05mol/L, 0.50mol/L nickel nitrate, The ferric nitrate of 0.50mol/L, the cerous nitrate of 0.50mol/L, 0.25mol/L cobalt nitrate, the mixing of 0.25mol/L copper nitrate are molten Liquid puts into pretreated ozone oxidation catalyst carrier material in above-mentioned mixing salt solution according to the dosage of 90g/L, Concussion dipping 48h, dipping filter out dipping object after the completion in 70 DEG C of water-bath, repeat above-mentioned dip operation 3 times, spare；
Calcination process step, the Muffle kiln roasting 4h for being 400 DEG C in maturing temperature by the solid particle after multiple dipping, Obtain ozone oxidation catalyst.
(2), below by specific embodiment, the method provided invention is described in detail, used in each embodiment Catalytic ozonation tower be the second microporous aeration disc provided by the invention be located at the first microporous aeration disc to water outlet height At 1/2, and the catalytic ozonation tower with 2 oxidant dosing mouths.
Embodiment 5
Waste water is derived from certain coal gas project project secondary settling tank biological oxidation water outlet of Poten Environment Group Co., Ltd., Waste water main indicator is CODCrFor 650.0mg/L, 400 times of coloration, pH value 7.78, UV254It is 7.120.
Keep coal gasification waste water pH value constant, adding PFS is 500mg/L, is stirred 0.5 minute with 150 revs/min of revolving speed Afterwards, the APAM of 5mg/L is added, is continued after being stirred 0.5 minute with 150 revs/min of revolving speed, lowers revolving speed to 35 revs/min, stirs 30 After minute, stopping stirring being filtered after staticly settling 30min；
Keep coagulative precipitation tank water outlet pH value constant, ozone oxidation catalyst prepared by embodiment 1, dosage 50g/L, Ozone reaction continuous aeration, ozone dosage 300mg/L, hydrogen peroxide dosage be 60mg/L, reaction time 50min, it is smelly The reflux ratio of the interior cyclic design of oxygen catalysis oxidizing tower is 4:5；
After being handled by the above each unit, effluent index that treated is CODCrFor 35.0mg/L, 4 times of coloration, UV254For 0.183；Water-quality COD after processingCrRemoval rate be 94.6%, the removal rate of coloration is 99.0%, UV254Removal rate be 97.4%.
Embodiment 6
Waste water is derived from certain coal gas project project secondary settling tank biological oxidation water outlet of Poten Environment Group Co., Ltd., Waste water main indicator is CODCrFor 655.2mg/L, 400 times of coloration, pH value 7.8, UV254It is 7.250.
Coal gasification waste water pH value is adjusted to 9 with sodium hydroxide, and adding PAC is 800mg/L, is stirred with 100 revs/min of revolving speed After 1.0 minutes, add the CPAM of 10mg/L, continue after being stirred 1.0 minutes with 100 revs/min of revolving speed, lower revolving speed to 50 turns/ Point, after twenty minutes, stopping stirring being filtered after staticly settling 30min for stirring；
Coagulative precipitation tank is adjusted with dilute sodium hydroxide and is discharged pH value to 9, and ozone oxidation catalyst prepared by embodiment 2 is thrown Dosage is 60g/L, ozone reaction continuous aeration, ozone dosage 260mg/L, and hydrogen peroxide dosage is 50mg/L, when reaction Between be 40min, the reflux ratio of the interior cyclic design of catalytic ozonation tower is 3:5；
After being handled by the above each unit, effluent index that treated is CODCrFor 40.3mg/L, 4 times of coloration, UV254For 0.195；Water-quality COD after processingCrRemoval rate be 93.8%, the removal rate of coloration is 99.0%, UV254Removal rate be 97.3%.
Embodiment 7
Waste water is derived from certain coal gas project project secondary settling tank biological oxidation water outlet of Poten Environment Group Co., Ltd., Waste water main indicator is CODCrFor 640mg/L, 400 times of coloration, pH value 7.4, UV254It is 7.135.
Coal gasification waste water pH value is adjusted to 5 with acetic acid, and adding PAFC is 200mg/L, stirs 2.0 with 300 revs/min of revolving speed After minute, the HPAM of 15mg/L is added, continued after being stirred 2.0 minutes with 300 revs/min of revolving speed, lower revolving speed to 80 revs/min, After ten minutes, stopping stirring being filtered after staticly settling 30min for stirring；
With sodium carbonate adjusting coagulative precipitation tank water outlet pH value to 7, ozone oxidation catalyst prepared by embodiment 3, dosage For 100g/L, ozone reaction continuous aeration, ozone dosage 280mg/L, hydrogen peroxide dosage is 62mg/L, and the reaction time is 60min, the reflux ratio of the interior cyclic design of catalytic ozonation tower are 1:1；
After being handled by the above each unit, effluent index that treated is CODCrFor 43.6mg/L, 4 times of coloration, UV254For 0.206；Water-quality COD after processingCrRemoval rate be 93.2%, the removal rate of coloration is 99.0%, UV254Removal rate be 97.1%.
Embodiment 8
Waste water is derived from certain coal gas project project secondary settling tank biological oxidation water outlet of Poten Environment Group Co., Ltd., Waste water main indicator is CODCrFor 661.0mg/L, 400 times of coloration, pH value 7.6, UV254It is 7.027.
Coal gasification waste water pH value is adjusted to 5 with nitric acid, and adding AS is 1000mg/L, stirs 3.0 with 150 revs/min of revolving speed After minute, the CPAM of 10mg/L is added, continued after being stirred 2.0 minutes with 200 revs/min of revolving speed, lower revolving speed to 100 revs/min, After stirring 15 minutes, stopping stirring being filtered after staticly settling 30min；
With quick lime adjusting coagulative precipitation tank water outlet pH value to 8, ozone oxidation catalyst prepared by embodiment 4, dosage For 120g/L, ozone reaction continuous aeration, ozone and chlorine dioxide dosage are respectively 220mg/L and 80mg/L, reaction time For 45min, the reflux ratio of the interior cyclic design of catalytic ozonation tower is 6:5；
After being handled by the above each unit, effluent index that treated is CODCrFor 45.4mg/L, 4 times of coloration, UV254For 0.169；Water-quality COD after processingCrRemoval rate be 93.1%, the removal rate of coloration is 99.0%, UV254Removal rate be 97.6%.
Embodiment 9
Waste water is derived from certain coal gas project project secondary settling tank biological oxidation water outlet of Poten Environment Group Co., Ltd., Waste water main indicator is CODCrFor 650.4mg/L, 400 times of coloration, pH value 7.7, UV254It is 7.231.
Coal gasification waste water pH value is adjusted to 4 with citric acid, and adding PAS is 100mg/L, is stirred with 200 revs/min of revolving speed After 1.5 minutes, add the APAM of 25mg/L, continue after being stirred 1.5 minutes with 200 revs/min of revolving speed, lower revolving speed to 30 turns/ Point, after twenty minutes, stopping stirring being filtered after staticly settling 30min for stirring；
With magnesium chloride adjusting coagulative precipitation tank water outlet pH value to 7, ozone oxidation catalyst prepared by embodiment 3, dosage For 150g/L, ozone reaction continuous aeration, ozone dosage 240mg/L, sodium hypochlorite dosage is 100mg/L, when reaction Between be 60min, the reflux ratio of the cyclic design of catalytic ozonation tower is 6:5；
After being handled by the above each unit, effluent index that treated is CODCrFor 36.8mg/L, 4 times of coloration, UV254For 0.196；Water-quality COD after processingCrRemoval rate be 94.3%, the removal rate of coloration is 99.0%, UV254Removal rate be 97.3%.
Embodiment 10
Waste water is derived from certain coal gas project project secondary settling tank biological oxidation water outlet of Poten Environment Group Co., Ltd., Waste water main indicator is CODCrFor 650.5mg/L, 400 times of coloration, pH value 7.7, UV254It is 7.273.
Coal gasification waste water pH value is adjusted to 8 with calcium chloride, and adding AS is 100mg/L, and adding PFS is 400mg/L, with 200 Rev/min revolving speed stir 1.0 minutes after, add the APAM of 15mg/L, add the HPAM of 1mg/L, continue to turn with 200 revs/min After speed stirring 1.0 minutes, lower revolving speed to 40 revs/min, after twenty minutes, stopping stirring being filtered after staticly settling 30min for stirring；
With sodium carbonate adjusting coagulative precipitation tank water outlet pH value to 8, ozone oxidation catalyst prepared by embodiment 1, dosage For 130g/L, ozone reaction continuous aeration, ozone dosage 210mg/L, chlorine addition amount is 120mg/L, and the reaction time is 40min, the reflux ratio of the interior cyclic design of catalytic ozonation tower are 3:5；
After being handled by the above each unit, effluent index that treated is CODCrFor 47.2mg/L, 4 times of coloration, UV254For 0.210；Water-quality COD after processingCrRemoval rate be 92.7%, the removal rate of coloration is 99.0%, UV254Removal rate be 97.1%.
Embodiment 11
Waste water is derived from certain coal gas project project secondary settling tank biological oxidation water outlet of Poten Environment Group Co., Ltd., Waste water main indicator is CODCrFor 648.4mg/L, 400 times of coloration, pH value 7.7, UV254It is 7.036.
Coal gasification waste water pH value is adjusted to 6 with nitric acid, and adding PAC is 300mg/L, and adding PAFC is 300mg/L, with 260 Rev/min revolving speed stir 2.0 minutes after, add the HPAM of 10mg/L, continue after being stirred 2.5 minutes with 200 revs/min of revolving speed, Lower revolving speed to 60 revs/min, after twenty minutes, stopping stirring being filtered after staticly settling 30min for stirring；
Coagulative precipitation tank is adjusted with sulfuric acid and is discharged pH value to 7, and ozone oxidation catalyst prepared by embodiment 2, dosage is 80g/L, ozone reaction continuous aeration, ozone dosage 160mg/L, hydrogen peroxide dosage are 200mg/L, and the reaction time is 40min, the reflux ratio of the interior cyclic design of catalytic ozonation tower are 6:5；
After being handled by the above each unit, effluent index that treated is CODCrFor 44.8mg/L, 4 times of coloration, UV254For 0.196；Water-quality COD after processingCrRemoval rate be 93.1%, the removal rate of coloration is 99.0%, UV254Removal rate be 97.2%.
Embodiment 12
Waste water is derived from certain coal gas project project secondary settling tank biological oxidation water outlet of Poten Environment Group Co., Ltd., Waste water main indicator is CODCrFor 654.5mg/L, 400 times of coloration, pH value 7.8, UV254It is 7.116.
Coal gasification waste water pH value is adjusted to 8 with sodium hydroxide, and adding PAC is 200mg/L, and adding PAFC is 500mg/L, is thrown Adding PFS is that 300mg/L is added the HPAM of 5mg/L, add 10mg/L's after being stirred 0.5 minute with 200 revs/min of revolving speed APAM adds the CPAM of 5mg/L, continues after being stirred 2.5 minutes with 150 revs/min of revolving speed, lowers revolving speed to 80 revs/min, stirs After 30 minutes, stopping stirring being filtered after staticly settling 30min；
With citric acid adjusting coagulative precipitation tank water outlet pH value to 7, ozone oxidation catalyst prepared by embodiment 4, dosage For 20g/L, ozone reaction continuous aeration, ozone dosage 290mg/L, hydrogen peroxide dosage is 100mg/L, and the reaction time is 30min, the reflux ratio of the interior cyclic design of catalytic ozonation tower are 6:5；
After being handled by the above each unit, effluent index that treated is CODCrFor 46.2mg/L, 4 times of coloration, UV254For 0.195；Water-quality COD after processingCrRemoval rate be 93.0%, the removal rate of coloration is 99.0%, UV254Removal rate be 97.3%.
It should be noted that the processing water of each processing unit of waste water is certain in actual waste water processing engineering 's.Those skilled in the art can determine the dosage of required reagent according to the amount of the processing waste water of each unit, usually each The dosage of unit reagent can be calculated with the dosage of every liter of waste water.Explanation is needed further exist for, COD represents chemistry and needs Oxygen amount refers under certain condition, the amount of oxidant consumed by reducing substances in 1L water sample is aoxidized, with the mass concentration of oxygen (as unit of mg/L) is indicated.The standard method for measuring COD is potassium dichromate method.The change measured with potassium dichromate method Oxygen demand is learned CODCr。
As can be seen from the above embodiments, coal gasification waste water is after method processing of the invention, and effluent index is much higher than " sewage is comprehensive Close discharge standard " (GB 8978-1996) first discharge standard, and the process is easy to operate, in practical applications, accounts for Ground area is small, is suitble to apply in much creating or proposing mark transformation project.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all Any modification, equivalent replacement, improvement and so within the spirit and principles in the present invention, are all contained in protection scope of the present invention It is interior.

Claims (8)

1. a kind of method of gas treatment waste water, which comprises the following steps:
The pH value of coal gasification waste water is adjusted to 4~10, carries out coagulating kinetics later, it is upper by being obtained through coagulating kinetics It after the pH value of clear liquid is adjusted to 7~9, is transported in catalytic ozonation tower and carries out catalytic ozonation processing, and to ozone Oxidant is added in catalysis oxidizing tower；Circulation in carrying out simultaneously；Residence time of the supernatant in catalytic ozonation tower is 10 ~60 minutes；Catalyst in catalytic ozonation tower is Poten-SOT type ozone oxidation catalyst；Ozone and oxidant are in institute Stating the dosage in the supernatant in oxidizing tower is respectively 50~350mg/L and 50~300mg/L；
The catalytic ozonation tower includes oxidizing tower ontology, ozone generator, circulating pump and tail gas breaking plant；
The oxidizing tower ontology includes the first microporous aeration disc, the second microporous aeration disc, catalyst layer, water inlet, water outlet, extremely A few oxidant dosing mouth, exhaust outlet, circulation water inlet and circulating outlet；
First microporous aeration disc is located at oxidizing tower body bottom portion；Second microporous aeration disc is located above the first microporous aeration disc；It urges Agent layer is located above the second microporous aeration disc；First microporous aeration disc and the second microporous aeration disc pass through pipeline and ozone respectively Generator is connected；
It is disposed with from the bottom to top on oxidizing tower this body sidewall between the first microporous aeration disc and the second microporous aeration disc Water inlet and circulation water inlet；Circulating outlet is disposed on tower body side wall above catalyst layer from the bottom to top and is gone out The mouth of a river；4 oxidant dosing mouths are provided on oxidizing tower this body sidewall between water inlet and circulating outlet, and are aoxidized Agent dosing mouth is distributed vertically on this body sidewall of oxidizing tower；Oxidizing tower bodies top is provided with exhaust outlet, exhaust outlet passes through pipe Road is connected with tail gas breaking plant；The water inlet end of circulating pump is connected by pipeline with circulating outlet, the water outlet of circulating pump End is connected by pipeline with circulation water inlet；
Second microporous aeration disc is located at the first microporous aeration disc at the 1/2 of water outlet height；
The Poten-SOT type ozone oxidation catalyst is made by following steps:
Ozone oxidation catalyst carrier is pre-processed；The pretreatment is first to carry out ozone oxidation catalyst carrier at least Primary washing, then it is immersed in 1~48h in acid solution, it is washed out to neutrality, is finally dried；
Pretreated ozone oxidation catalyst carrier is subjected to impregnation at least once, the impregnation is that will pre-process Ozone oxidation catalyst carrier afterwards is immersed in dipping solution, and 20~100 DEG C of 6~48h of immersion are dried later；It is described Dipping solution is nitrate, sulfate, acetate or chlorination containing metallic elements at least three kinds of in manganese, nickel, iron, cerium, cobalt and copper The mixed solution of object；Concentration of at least three kinds of metallic elements in dipping solution is respectively 0.01~1.00mol/L；
Ozone oxidation catalyst carrier after dipping is subjected to calcination process；
The ozone oxidation catalyst carrier is selected from granular porous ceramics, granulated activated aluminium oxide, particulate molecular sieve, coal Pilum shaped activated carbon, graininess active fruit shell carbon or the more silicon clinoptilolites of graininess, and its partial size is 3~6mm, specific surface area ≥250m2/ g, compression strength > 100N, bulk density > 0.17g/mL.
2. the method as described in claim 1, which is characterized in that the pH value of coal gasification waste water is adjusted to 6~9.
3. the method as described in claim 1, which is characterized in that the dipping solution is 6 kinds in manganese, nickel, iron, cerium, cobalt and copper The nitrate of metallic element, sulfate, acetate or chloride mixed solution, wherein manganese, nickel, iron, cerium, cobalt and copper The ratio between the amount of substance be (1~50): (1~50): (1~50): (1~50): (1~30): (1~30), and manganese, nickel, iron, The concentration of cerium, cobalt and copper in dipping solution is respectively 0.01~0.50mol/L.
4. the method as described in claim 1, which is characterized in that the pretreatment is first to carry out ozone oxidation catalyst carrier It washes, then is immersed in the nitric acid solution of 0.01~1.00mol/L 10~30 hours at least once, is washed out into Property, finally it is dried.
5. method as claimed in claim 4, which is characterized in that the ozone oxidation catalyst carrier after washing is immersed in 0.05 10~24 hours in the nitric acid solution of~0.15mol/L.
6. the method as described in claim 1, which is characterized in that the coagulating kinetics are first to be added into coagulative precipitation tank Inorganic coagulant is stirred 0.5~3.0 minute with 100~300 revs/min of revolving speed, then organic-flocculation is added into coagulative precipitation tank Agent is stirred 0.5~3.0 minute with 100~300 revs/min of revolving speed, adjusts revolving speed later to 30~100 revs/min, and stirring 10~ 30 minutes, last quiescent setting.
7. method as claimed in claim 6, which is characterized in that the inorganic coagulant be aluminium polychloride, bodied ferric sulfate, At least one of polyaluminum ferric chloride, polyaluminium sulfate, aluminum sulfate；The organic flocculant be cationic polyacrylamide, At least one of anionic polyacrylamide, polyacrylamide of partial hydrolysis；The inorganic coagulant and organic wadding Solidifying dosage of the agent in the coal gasification waste water for mixing up pH value is respectively 100~1000mg/L and 1~30mg/L；Oxidant was At least one of hydrogen oxide, sodium hypochlorite, chlorine dioxide and chlorine.
8. the method as described in claim 1, which is characterized in that the reflux ratio of the interior circulation is 3:5~6:5.
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