CN106467344A - Water treatment facilities for high saline sewage qualified discharge - Google Patents
Water treatment facilities for high saline sewage qualified discharge Download PDFInfo
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Abstract
The present invention discloses a kind of water treatment facilities for high saline sewage qualified discharge, including catalysis oxidation pond, oxidation-stabilized pond, afterwards biochemical BAF pond, clear water reserviors, collecting-tank and filter, described catalysis oxidation pond is filled with ozone catalytic granule with fixed bed form, and the group of following weight portion is grouped into：Activated alumina is mixed in stirring mixer with copper oxide, Polyethylene Glycol, polyvinyl alcohol, titanium dioxide, hydroxypropyl cellulose, manganese dioxide so that uniformly mixed copper oxide, Polyethylene Glycol, polyvinyl alcohol, titanium dioxide, hydroxypropyl cellulose, manganese dioxide are covered in described activated alumina particle surface and form catalyst mother bulb；Again catalyst mother bulb is dried successively, roasting obtains described resistance to high salt ozone catalyst.Operating cost of the present invention is low, simple to operate, stable, and obtains the purpose of efficient degradation organic pollution, can achieve the petroleum chemical industry high saline sewage advanced treating under low cost and qualified discharge.
Description
Technical field
The present invention relates to a kind of water treatment facilities for high saline sewage qualified discharge, belong to petrochemical effluent technical field.
Background technology
Advanced treatment process currently used for the high saline sewage of petrochemical industry mainly has biological oxidation process and physical chemistry advanced oxidation processes two class, biological oxidation process is with MBR technique as representative, it is disadvantageous in that high saliferous deeply treating wastewater biodegradability extreme difference (BOD ＜ 10), biochemical process effect limited it is impossible to reach the requirement of sewage discharge primary standard；Advanced oxidation processes include the oxidation of ozone directly contact, Fenton reagent etc., and it is disadvantageous in that, and treatment effect is unstable, operating cost is high, produce secondary pollution etc..
Content of the invention
It is an object of the present invention to provide a kind of water treatment facilities for high saline sewage qualified discharge, the water treatment facilities operating cost that this is used for high saline sewage qualified discharge is low, simple to operate, stable, and obtain purpose, the petroleum chemical industry high saline sewage advanced treating under achievable low cost and the qualified discharge of efficient degradation organic pollution.
For reaching above-mentioned purpose, the technical solution used in the present invention is：A kind of water treatment facilities for high saline sewage qualified discharge，Including catalysis oxidation pond、Oxidation-stabilized pond、Biochemical BAF pond afterwards、Clear water reserviors、Collecting-tank and filter，Described catalysis oxidation pond、Oxidation-stabilized pond、Biochemical BAF pond and clear water reserviors pass sequentially through transfer conduit and connect afterwards，Described filter is connected to inside catalysis oxidation pond by inlet channel，One ozonator is connected to inside catalysis oxidation pond by gas pipeline，Described clear water reserviors are provided with inlet opening、Apopore and return port，The inlet opening of described clear water reserviors is connected by transfer conduit with rear biochemistry BAF pond，The apopore of described clear water reserviors is connected to a backwashing pump one end，This backwashing pump other end is connected to catalysis oxidation pond by reflux line、Afterwards inside biochemical BAF pond，Described catalysis oxidation pond is filled with ozone catalytic granule with fixed bed form，Described collecting-tank is located at the catalysis oxidation pond side opposite with oxidation-stabilized pond，It is disposed with elevator pump and filter between this collecting-tank and catalysis oxidation pond；
Described ozone catalytic granule is grouped into by the group of following weight portion：
By described particle diameter be 2～4mm 88.7～91.3 parts of activated alumina particle and 1.2～1.5 parts of copper oxide, 4～7 parts of Polyethylene Glycol, 1.5～2 parts of polyvinyl alcohol, 0.8～1 part of titanium dioxide, 0.3～0.5 part of hydroxypropyl cellulose, 0.2～0.4 part of manganese dioxide mixes in stirring mixer, so that uniform 1.2～1.5 parts of mixed copper oxide, 4～7 parts of Polyethylene Glycol, 1.5～2 parts of polyvinyl alcohol, 0.8～1 part of titanium dioxide, 0.3～0.5 part of hydroxypropyl cellulose, 0.2～0.4 part of manganese dioxide is covered in described activated alumina particle surface and forms catalyst mother bulb；Again catalyst mother bulb is dried successively, roasting obtains described ozone catalytic granule.
In technique scheme, further improved technical scheme is as follows：
As preferred, vertically it is provided with a dividing plate in described catalysis oxidation pond, thus catalysis oxidation pond is divided into left and right chamber, described catalysis oxidation pond lower horizontal is provided with a sieve plate, the lower end of this dividing plate is installed to the upper surface of sieve plate, and described ozone catalytic granule is located above sieve plate and is located at dividing plate both sides.
Preferably, described ozonator is connected to the bottom in catalysis oxidation pond by gas pipeline.
Preferably, described drying keeps 4～6 hours under the conditions of 100～120 DEG C.
Preferably, described roasting is incubated 7～9 hours under the conditions of 350～520 DEG C.
Because technique scheme is used, the present invention compared with prior art has following advantages and effect：
1, the present invention is used for the water treatment facilities of high saline sewage qualified discharge, its catalytic ozonation technology compares other chemical oxidization methods, reaction rate is rapid, produce the hydroxyl radical free radical of non-selectivity active in a large number, multiple pollutant in oxidized waste water, improve the biodegradability of waste water, oxidation water outlet enters interior circulation BAF, filtration in biological bed, under bioflocculation and biological adsorption effect, the materials such as the Organic substance containing in waste water are adsorbed oxidation further, the method effectively combines the biochemical treatment advantage with advanced oxidation high efficiency with low cost, improve the feasibility of RO concentrated water advanced treating；Secondly, improve the tolerance to the high saline sewage of petrochemical industry, so that in the catalytic oxidation treatment process to saline sewage, catalyst ozone produces active hydroxyl radical free radical, keeps good effect to the biodegradability of the removal of waste water COD, decolouring, de- stench, degraded toxic pollutant and raising waste water.
2nd, the present invention is used for the water treatment facilities of high saline sewage qualified discharge, its physical capacity of resistance to salt is strong, normally can use in the TDS no more than waste water of 8000mg/L, catalyst activity is high, low cost, and preparation method is simple, therefore for catalytic ozonation technology, the extensive application tool in saline sewage advanced treating is of great significance.
Brief description
Accompanying drawing 1 is used for the water treatment facilities structural representation of high saline sewage qualified discharge for the present invention；
Accompanying drawing 2 is the partial structural diagram of accompanying drawing 1.
In the figures above：1st, catalysis oxidation pond；2nd, oxidation-stabilized pond：3rd, biochemical BAF pond afterwards；4th, clear water reserviors；41st, inlet opening；42nd, apopore；5th, transfer conduit；6th, elevator pump；7th, inlet channel；8th, ozonator；9th, gas pipeline；10th, reflux line；11st, backwashing pump；12nd, ozone catalytic granule；13rd, dividing plate；14th, sieve plate；15th, collecting-tank；16th, filter.
Specific embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1～4：A kind of water treatment facilities for high saline sewage qualified discharge，Including catalysis oxidation pond 1、Oxidation-stabilized pond 2、Biochemical BAF pond 3 afterwards、Clear water reserviors 4、Collecting-tank 15 and filter 16，Described catalysis oxidation pond 1、Oxidation-stabilized pond 2、Biochemical BAF pond 3 and clear water reserviors 4 pass sequentially through transfer conduit 5 and connect afterwards，Described filter 16 is connected to inside catalysis oxidation pond 1 by inlet channel 7，One ozonator 8 is connected to inside catalysis oxidation pond 1 by gas pipeline 9，Described clear water reserviors 4 are provided with inlet opening 41、Apopore 42，The inlet opening 41 of described clear water reserviors 4 is connected by transfer conduit 5 with rear biochemistry BAF pond 3，The apopore 42 of described clear water reserviors 4 is connected to a backwashing pump 11 one end，This backwashing pump 11 other end is connected to catalysis oxidation pond 1 by reflux line 10、Afterwards inside biochemical BAF pond 3，Described catalysis oxidation pond 1 is filled with ozone catalytic granule 12 with fixed bed form，Described collecting-tank 15 is located at catalysis oxidation pond 1 side opposite with oxidation-stabilized pond 2，It is disposed with elevator pump 6 and filter 16 between this collecting-tank 15 and catalysis oxidation pond 1；
Described ozone catalytic granule 12 is grouped into by the group of following weight portion, as shown in table 1：
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Activated alumina particle | 90 parts | 89.5 parts | 89 parts | 91 parts |
| 1.2～1.5 parts of copper oxide | 1.25 part | 1.4 part | 1.2 part | 1.3 part |
| 4～7 parts of Polyethylene Glycol | 5.2 part | 6 parts | 4.5 part | 6.2 part |
| 1.5～2 parts of polyvinyl alcohol | 1.5 part | 1.8 part | 2 parts | 1.6 part |
| 0.8～1 part of titanium dioxide | 1 part | 0.9 part | 0.95 part | 0.8 part |
| 0.3～0.5 part of hydroxypropyl cellulose | 0.45 part | 0.38 part | 0.5 part | 0.35 part |
| 0.2～0.4 part of manganese dioxide | 0.3 part | 0.2 part | 0.25 part | 0.32 part |
Described activated alumina particle particle diameter is 2～4mm；
88.7～91.3 parts of the activated alumina particle that described particle diameter is 2～4mm is mixed in stirring mixer with 1.2～1.5 parts of copper oxide, 4～7 parts of Polyethylene Glycol, 1.5～2 parts of polyvinyl alcohol, 0.8～1 part of titanium dioxide, 0.3～0.5 part of hydroxypropyl cellulose, 0.2～0.4 part of manganese dioxide so that uniformly 1.4～1.6 parts of mixed copper oxide, 0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol are covered in described activated alumina particle surface and form catalyst mother bulb；Again catalyst mother bulb is dried successively, roasting obtains described ozone catalytic granule 12.
Activated alumina particle particle diameter is 2～4mm；
88.7～91.3 parts of the activated alumina particle that described particle diameter is 2～4mm is mixed in stirring mixer with 1.4～1.6 parts of copper oxide, 0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol so that uniformly 1.4～1.6 parts of mixed copper oxide, 0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol are covered in described activated alumina particle surface and form catalyst mother bulb；Again catalyst mother bulb is dried successively, roasting obtains described ozone catalytic granule 12.
Vertically it is provided with a dividing plate 13 in above-mentioned catalysis oxidation pond 1, thus catalysis oxidation pond is divided into left and right chamber, described catalysis oxidation pond 1 lower horizontal is provided with a sieve plate 14, the lower end of this dividing plate 13 is installed to the upper surface of sieve plate 14, and described ozone catalytic granule 12 is located at sieve plate 14 top and is located at dividing plate 13 both sides.
Above-mentioned ozonator 8 is connected to the bottom in catalysis oxidation pond by gas pipeline 9.
Above-mentioned drying keeps 4～6 hours under the conditions of 100～120 DEG C.
Above-mentioned roasting is incubated 7～9 hours under the conditions of 350～520 DEG C
The preparation method of the ozone catalytic granule 12 of above-described embodiment, comprises the following steps：
Step one, 88.7～91.3 parts of activated alumina distilled water are cleaned for several times to remove the impurity on its surface, and be dried to quality constant weight, the particle diameter of described activated alumina is 2～4mm；
Step 2, 88.7～91.3 parts of activated aluminas that obtain step one and 1.2～1.5 parts of copper oxide, 4～7 parts of Polyethylene Glycol, 1.5～2 parts of polyvinyl alcohol, 0.8～1 part of titanium dioxide, 0.3～0.5 part of hydroxypropyl cellulose, 0.2～0.4 part of manganese dioxide mixes in stirring mixer, so that uniform 1.2～1.5 parts of mixed copper oxide, 4～7 parts of Polyethylene Glycol, 1.5～2 parts of polyvinyl alcohol, 0.8～1 part of titanium dioxide, 0.3～0.5 part of hydroxypropyl cellulose, 0.2～0.4 part of manganese dioxide is covered in described activated alumina particle surface and forms catalyst mother bulb；
Step 3, take out described catalyst mother bulb from stirring mixer, after drying at room temperature, put into baking oven, be dried under the conditions of 100～120 DEG C and obtain dried catalyst mother bulb；
Step 4, dried catalyst mother bulb is put in Muffle furnace, roasting under the conditions of 350～520 DEG C obtains resistance to high salt ozone catalyst.
In above-mentioned steps three, under the conditions of 100～120 DEG C, drying time is 5 hours, and in above-mentioned steps four, under the conditions of 350～520 DEG C, roasting time is 8 hours.
Ozone catalytic particulate catalytic effect assessment of the present invention, experimental technique data is shown in Table 2：
In the test of dynamic continuous flow catalytic ozonation, catalyst amountses are 1.5L, ozone dosage 100mg/L, hydraulic detention time 1h, utilize gas flowmeter to control ozone dosage, by peristaltic pump continuum micromeehanics in experiment.After running 3 cycle catalytic effect stabilities, repeatedly COD is measured by sampling, averages.
Experiment condition：Dynamic continuous flow operational mode, ozone dosage 100mg/L, HRT=1h.
Water inlet source：Certain factory RO concentrated water, COD about 350mg/L, TDS are 3500mg/L.
The Contrast on effect of the different ozone catalyst catalysis oxidation RO concentrated water of table 2
From table 2, data understands, with respect to Zhonghai Asphalt's conventional alumina ozone catalyst, resistance to high salt ozone catalyst catalysis oxidation RO concentrated water, it is 100mg/L in ozone dosage, hydraulic detention time is under 1h service condition, COD clearance is up to 34.2%, and ozone efficiency is 1.1, far superior to conventional ozone catalyst.
The present embodiment is used for the water treatment facilities of high saline sewage qualified discharge, and specific implementation step is as follows：
(1), high saline sewage after pretreatment is lifted into filter through pump；
(2), filter water outlet gravity flow enters catalytic ozonation pond, adds ozone simultaneously, carry out catalytic ozonation reaction into catalytic ozonation pond；
(3), ozone catalytic oxidation unit water outlet gravity flow enters oxidation-stabilized pond；
(4) after, water outlet gravity flow in oxidation-stabilized pond enters, biochemistry BAF unit, carries out biochemical reaction；
(5), biochemical BAF unit water outlet gravity flow enters clear water reserviors, qualified discharge afterwards；
Wherein, in step (1), filter water outlet indicator of suspended solids controls within 20mg/L；
Every liter of sewage ozone dosage 50mg in step (2), added ozonized air concentration is 80～120mgO3/L gas, the catalytic ozonation apparent time of staying (HRT) is 1.5h, and in catalytic ozonation pond, catalyst exists as a fixed bed.
Not enough for above-mentioned the problems of the prior art, the present invention proposes high treating effect, stable, operating cost is low, does not produce the petrochemical industry high saline sewage deep treatment method of secondary pollution.Rear biochemistry BAF technique is combined using catalytic ozonation, biological oxidation unit employs interior circulation BAF technology, catalytic ozonation technical matters are simple and convenient to operate, and can be accomplished the end in view by gas flowmeter flexibly changing ozone amount according to influent quality situation；Interior circulation BAF technology can maintain higher Biomass and biological activity to keep biochemical ability in lean auxotype sewage.In order to ensure the two function efficient combination, in ozone catalytic oxidation unit front end, increase more medium filter, remove oil removal；And it is provided with oxidation-stabilized pond between two processing units, to guarantee being properly completed and preventing the microbial activity in biochemical unit after remaining oxidizing agent suppression of advanced oxidation processes, reach the purpose having complementary functions.Operating cost is low, simple to operate, stable, and obtains the purpose of efficient degradation organic pollution, can achieve the petroleum chemical industry high saline sewage advanced treating under low cost and qualified discharge.
The present invention adopts ozone catalytic granule, ozone catalytic is produced hydroxyl radical free radical, reduce the activation energy of hydroxyl radical free radical oxidation reaction simultaneously, make an Organic substance part for difficult degradation in high saline sewage modified, the easily biochemical Organic substance of small molecule is become by macromole biorefractory organic, directly mineralising removes a part, or direct oxidation is decomposed into H2O and CO2.
Pretreated high saline sewage is first entered collecting-tank by the inventive method, it is lifted into filter through pump, filter water outlet indicator of suspended solids is less than 20mg/L it is therefore an objective to remove the float in high saline sewage, thus the dirt of the oxidation load and ozone catalyst reducing catalytic ozonation pond is blocked up；Filter water outlet gravity flow enters the catalytic ozonation pond being filled with metal ion catalyst, adds 50mgO simultaneously3The ozonized air of/L water, in the presence of catalyst, the ozone of high oxidative is changed into that oxidisability is higher and the selective hydroxyl radical free radical of non-oxidation, reduce the activation energy of hydroxyl radical free radical oxidation reaction simultaneously, hydroxyl radical free radical will be modified for a hardly degraded organic substance part remaining in high saline sewage, the easily biochemical Organic substance of small molecule is become by macromole biorefractory organic, a part directly decompose by mineralising, or direct oxidation is H2O and CO2；Ozone oxidation water outlet gravity flow enters oxidation-stabilized pond, through the 1h time of staying, makes water stabilization and naturally clears up excessive ozone；After the water outlet gravity flow of oxidation-stabilized pond enters, biochemistry BAF unit carries out biochemical treatment, thus reaching the advanced treating purpose of high saline sewage.
The present embodiment is used for the water treatment facilities of high saline sewage qualified discharge, and comprehensive treatment effect is as shown in table 3：
The water analysis data of table 3 embodiment
As table 3 instance data is learnt, the present invention has high efficiency to Organic substance in petrochemical industry high saline sewage advanced treatment of waste water.Wherein, catalytic ozonation carries out catalysis generation hydroxyl radical free radical by ion load type catalyst to ozone, and hardly degraded organic substance is carried out with advanced oxidation, COD clearance average out to 38%；Biochemical system carries out oxidation Decomposition using microorganism to dirty Organic substance in water afterwards, and COD clearance is 32%；COBR advanced treatment system is 59.4% to the total removal rate of COD.In sum, COBR has feasibility to petrochemical industry high saline sewage advanced treatment system qualified discharge.
Above-described embodiment only technology design to illustrate the invention and feature, be its object is to allow person skilled in the art will appreciate that present disclosure and to implement according to this, can not be limited the scope of the invention with this.All equivalence changes made according to spirit of the invention or modification, all should be included within the scope of the present invention.
Claims (5)
1. a kind of water treatment facilities for high saline sewage qualified discharge it is characterised in that：Including catalysis
Oxidation pond (1), oxidation-stabilized pond (2), afterwards biochemical BAF pond (3), clear water reserviors (4), collecting-tank (15)
With filter (16), described catalysis oxidation pond (1), oxidation-stabilized pond (2), afterwards biochemical BAF pond (3)
Pass sequentially through transfer conduit (5) with clear water reserviors (4) to connect, described filter (16) passes through inlet channel
(7) it is connected to catalysis oxidation pond (1) internal, an ozonator (8) passes through gas pipeline (9) even
It is connected to catalysis oxidation pond (1) internal, described clear water reserviors (4) are provided with inlet opening (41), apopore (42),
Transfer conduit (5) is passed through even with rear biochemistry BAF pond (3) in the inlet opening (41) of described clear water reserviors (4)
Connect, the apopore (42) of described clear water reserviors (4) is connected to a backwashing pump (11) one end, this backwashing pump (11)
The other end is connected to catalysis oxidation pond (1), afterwards biochemical BAF pond (3) inside by reflux line (10),
Described catalysis oxidation pond (1) is filled with ozone catalytic granule (12), described collecting-tank (15) with fixed bed form
Positioned at the side that catalysis oxidation pond (1) is opposite with oxidation-stabilized pond (2), this collecting-tank (15) and catalysis
It is disposed with elevator pump (6) and filter (16) between oxidation pond (1)；
Described ozone catalytic granule (12) is grouped into by the group of following weight portion：
By described particle diameter be 2～4mm 88.7～91.3 parts of activated alumina particle and 1.2～1.5 parts of copper oxide,
4～7 parts of Polyethylene Glycol, 1.5～2 parts of polyvinyl alcohol, 0.8～1 part of titanium dioxide, hydroxypropyl cellulose 0.3～0.5
Part, 0.2～0.4 part of manganese dioxide mixes in stirring mixer so that uniform mixed copper oxide 1.2～1.5
Part, 4～7 parts of Polyethylene Glycol, 1.5～2 parts of polyvinyl alcohol, 0.8～1 part of titanium dioxide, hydroxypropyl cellulose 0.3～0.5
Part, 0.2～0.4 part of manganese dioxide are covered in described activated alumina particle surface and form catalyst mother bulb；Again will
Catalyst mother bulb is dried successively, roasting obtains described ozone catalytic granule (12).
2. the water treatment facilities for high saline sewage qualified discharge according to claim 1, it is special
Levy and be：Vertically it is provided with a dividing plate (13) in described catalysis oxidation pond (1), thus by catalysis oxidation
Pond is divided into left and right chamber, and described catalysis oxidation pond (1) lower horizontal is provided with a sieve plate (14), this every
The lower end of plate (13) is installed to the upper surface of sieve plate (14), and described ozone catalytic granule (12) is located at sieve
Above plate (14) and positioned at dividing plate (13) both sides.
3. the water treatment facilities for high saline sewage qualified discharge according to claim 1, it is special
Levy and be：Described ozonator (8) is connected to the bottom in catalysis oxidation pond by gas pipeline (9).
4. the water treatment facilities for high saline sewage qualified discharge according to claim 1, it is special
Levy and be：Described drying keeps 4～6 hours under the conditions of 100～120 DEG C.
5. the water treatment facilities for high saline sewage qualified discharge according to claim 1, it is special
Levy and be：Described roasting is incubated 7～9 hours under the conditions of 350～520 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107673461A (en) * | 2017-10-10 | 2018-02-09 | 苏州聚智同创环保科技有限公司 | Sewage-treatment plant and method and system |
| CN115007143A (en) * | 2022-07-20 | 2022-09-06 | 北京清新环境技术股份有限公司 | Sewage treatment catalyst, and composite granulation method and application thereof |
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| CN104759286A (en) * | 2015-03-12 | 2015-07-08 | 苏州清然环保科技有限公司 | Ozone catalyst preparation method |
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| CN107673461A (en) * | 2017-10-10 | 2018-02-09 | 苏州聚智同创环保科技有限公司 | Sewage-treatment plant and method and system |
| CN115007143A (en) * | 2022-07-20 | 2022-09-06 | 北京清新环境技术股份有限公司 | Sewage treatment catalyst, and composite granulation method and application thereof |
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Application publication date: 20170301 |