CN107915310B - A kind of efficient catalytic sodium hypochlorite mid-water process craft based on composite catalyzing bed - Google Patents
A kind of efficient catalytic sodium hypochlorite mid-water process craft based on composite catalyzing bed Download PDFInfo
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
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Abstract
The efficient catalytic sodium hypochlorite sewerage disposing system based on composite catalyzing bed that the invention discloses a kind of, including oxidizing tower are provided with bed of activated carbon catalyst layer and molecular sieve catalyst bed in oxidizing tower.The invention also discloses a kind of efficient catalytic sodium hypochlorite mid-water process craft based on composite catalyzing bed.The present invention realizes the catalytic bed to the activation of sodium hypochlorite, effectively reduces the content of hardly degraded organic substance in middle water, realizes the advanced treating of middle water.Not only greatly improve the utilization efficiency of catalyst, significantly improve the oxidation effectiveness of sodium hypochlorite, mechanical strength and surface anti-pollution performance it is equal to effectively improving, avoid the loss of catalyst in use, effectively increase the stability of the technique.The technique has not only fully ensured that the utilization efficiency of catalyst, so that the catalytic bed can be used for the processing of a variety of municipal middle waters, while extending the service life of catalyst, so that the application of the technique is greatly improved.
Description
Technical field
The present invention relates to a kind of sodium hypochlorite sewerage disposing systems, specifically, are related to a kind of based on composite catalyzing bed
Efficient catalytic sodium hypochlorite sewerage disposing system and its technique, belong to sewerage disposing technical field.
Background technique
As current more and more water bodys are contaminated, and society is to increasing with the demand of water, and therefore, middle water returns
With an important channel for becoming current solution water difficulty.And middle water is usually biological tank water outlet, reaches secondary discharge standard,
Certain pollutant is still had in middle water, these pollutants are usually difficult to based on biodegradable organic matter, and such organic
Object will affect the subsequent use of middle water, at present due to lacking the minimizing technology of high efficiency low cost, and can cause to Treated sewage reusing centainly
Influence.
Chemical oxidization method, especially catalytic oxidation technique have degradation of organic substances high-efficient, the degradation advantages such as rapidly, can be with
It is difficult in water water body through biodegradable organic matter in fast degradation.Catalytic oxidation technologies include Wet Oxidation Process, Fenton/
The techniques such as class Fenton technology, catalytic ozonation technology and sodium hypochlorite catalytic oxidation technologies.Usual catalytic oxidation technologies need
The oxidizing potential of ozone, hydrogen peroxide or sodium hypochlorite is improved by specific means, thus to improve oxidation efficiency, at present
By limited means in due to heterogeneous catalysis have be easy to reaction system separation, not will cause secondary pollution, be catalyzed
The advantages that high-efficient, and the most common means of catalysis oxidation are applied to, heterogeneous catalysis is many kinds of, can be improved smelly
The oxidation susceptibility of the oxidants such as oxygen, hydrogen peroxide and sodium hypochlorite.And since hydrogen peroxide can not usually be prepared in situ, and ozone
Then use cost is excessively high, and therefore, the more other two kinds of oxidants of range applied by sodium hypochlorite are more wide in range.
Currently, the catalyst of sodium hypochlorite catalytic oxidation technique is usually the catalyst of nickel-loaded, pass through infusion process, mixing
Prepared by calcination method, main carriers have molecular sieve, zeolite and active carbon etc..By adulterating other special metals, can effectively mention
The catalytic performance of high catalyst, and it can be effectively improved carrier property, resistant to pollution performance of carrier etc. is improved, so that carrier is stablized
Property is improved.It can allow carrier while giving full play to heterogeneous medium, it is physical to increase absorption, filtering of carrier etc.
Energy.Study effective catalyst additive, in catalyst preparation process incorporation can improve simultaneously catalyst chemical property and
The special metal of physical property is the research hotspot of this field.
Summary of the invention
The technical problem to be solved by the present invention is to against the above deficiency, provide a kind of efficiently urging based on composite catalyzing bed
Change sodium hypochlorite sewerage disposing system and its technique, realizes the catalytic bed to the activation of sodium hypochlorite, effectively drop
The content of hardly degraded organic substance, realizes the advanced treating of middle water in low middle water.Not only greatly improve the utilization of catalyst
Efficiency, significantly improves the oxidation effectiveness of sodium hypochlorite, mechanical strength and surface anti-pollution performance it is equal to effectively improving, avoid
The loss of catalyst in use, effectively increases the stability of the technique.The technique has not only fully ensured that catalyst
Utilization efficiency so that the catalytic bed can be used for the processing of the municipal middle waters in more areas, while extending the use of catalyst
Period, so that the application of the technique is greatly improved.Its catalyst preparation process easily realizes that technical process scale can greatly may be used
It is small, it is easily controllable；The system, operation is simple, and daily maintenance is convenient, and processing cost is low.
In order to solve the above technical problems, the invention adopts the following technical scheme: it is a kind of based on the efficient of composite catalyzing bed
It is catalyzed sodium hypochlorite sewerage disposing system, including oxidizing tower, is provided with bed of activated carbon catalyst layer and molecule in the oxidizing tower
Sieve catalyst bed, the bed of activated carbon catalyst layer are located at the bottom of oxidizing tower, and the molecular sieve catalyst bed, which is located at, lives
The top of property Pd/carbon catalyst bed.
A kind of prioritization scheme, the oxidizing tower can be dismantled from middle part；It aoxidizes tower bottom and is equipped with liquid-distributing disk, can push away
Water is uniformly through bed in dynamic；The oxidizing tower is pillar oxidizing tower, and the oxidation tower height degree and base diameter ratio are more than 3:1.
The present invention also provides a kind of efficient catalytic sodium hypochlorite mid-water process craft based on composite catalyzing bed, including urge
Agent preparation step, catalyst includes nickel nitrate, ferric nitrate, magnesium nitrate in the catalyst preparation step；Nickel nitrate, nitric acid
Iron, magnesium nitrate mass ratio be 5:2:1.
The powder of nickel nitrate, ferric nitrate, magnesium nitrate is put into ball mill grinding mixing, will then mixed by a kind of prioritization scheme
Two parts of aqueous solution that powder is configured to 5% are closed, respectively wherein by molecular sieve and active carbon investment, after soaking 12h, is put into baking oven
105 DEG C of baking 6h, are then calcined with Muffle furnace, obtain activated-carbon catalyst and molecular sieve catalyst after cooling.
Further, the molecular sieve selects the molecular sieve of MCM41 type, and active carbon selects coconut husk class active carbon；
The calcination temperature of the activated-carbon catalyst is 400-500 DEG C, and calcination time 1-3h, molecular sieve catalyst is forged
Burning temperature is 600-800 DEG C, calcination time 3-5h.
Further, the specific surface area of the molecular sieve is more than 1000m2/ g, relative crystallinity are more than 90%, burning decrement
No more than 5%, aperture is distributed within the scope of 2-5nm.
The active carbon mesh number is 12-30 mesh, and intensity is more than 95%, and water content is no more than 5%, iodine sorption value 1100-
1200mg/g, specific surface area 1100-1150m2/g。
Further, including catalytic bed preparation step, in the catalytic bed preparation step, by activated-carbon catalyst and
Molecular sieve catalyst is filled into oxidizing tower.
Further, activated-carbon catalyst and molecular sieve catalyst are successively filled in oxidizing tower with the mass ratio of 1:1,
Activated-carbon catalyst is placed in oxidation tower bottom, and molecular sieve catalyst is placed in activated-carbon catalyst top.
Further, activated-carbon catalyst is first filled in oxidation tower bottom and be compacted, bed of activated carbon catalyst layer
Height accounts for the 15% of oxidizing tower, then molecular sieve catalyst is filled in oxidizing tower, molecular sieve catalyst bed height accounts for oxidation
The 15% of tower；Activated-carbon catalyst and molecular sieve catalyst need to load consolidation.
Further, including sodium hypochlorite catalytic oxidation stage, middle water and liquor natrii hypochloritis are mixed in advance, and
It is passed through afterwards from the bottom of oxidizing tower, middle water is stopped in oxidizing tower, and mean residence time 3-5h, centering water is catalyzed
Oxidation；Liquor natrii hypochloritis's concentration is normally controlled in 1-5%, and liquor natrii hypochloritis is to mix in pipeline with middle water hybrid mode, secondary
The volume ratio of sodium chlorate solution and middle water is 1:200-1000.
After the invention adopts the above technical scheme, compared with prior art, have the advantage that
(1) activated-carbon catalyst of the present invention also has excellent stability in addition to excellent catalytic activity
And oxidative resistance, while there is excellent mechanical strength, both can occur being pressed because of bed layer pressure to avoid activated-carbon catalyst
Broken situation, and high catalytic activity can be kept for a long time, reduce reaction operating cost；
(2) molecular sieve catalyst of the present invention has excellent catalytic activity, the molecular sieve catalytic of more simple nickel-loaded
Agent, catalytic activity are significantly increased, and have fully ensured that the utilization efficiency of catalyst；The stability of molecular sieve itself can obtain simultaneously
To being greatly improved, greatly reduces molecular sieve and lost because of current scour；
(3) catalyst preparation process of the present invention is without using extreme condition or difficult purchase reagent, catalyst preparation
Process easily realizes that technical process scale is changeable, easily controllable；
(4) recycled water advanced treatment technique of the present invention realizes the catalytic bed to the activation of sodium hypochlorite, has
Effect reduces the content of hardly degraded organic substance in middle water, realizes the advanced treating of middle water, which, which has not only fully ensured that, urges
The utilization efficiency of agent, so that the catalytic bed can be used for the processing of the municipal middle water in more areas, for the city in more areas
Middle water all has good COD and TOC removal rate, and applicability is wide, while extending the service life of catalyst, so that the technique
Application is greatly improved.
(5) present invention not only greatly improves the utilization efficiency of catalyst, significantly improves the oxidation effectiveness of sodium hypochlorite, machine
Tool intensity and surface anti-pollution performance it is equal to effectively improving, avoid the loss of catalyst in use, effectively improve
The stability of the technique, the recycled water advanced treatment system, operation is simple, and daily maintenance is convenient, and processing cost is low.It ties below
Closing drawings and examples, the present invention is described in detail.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of processing system of the present invention；
In figure,
1- oxidizing tower, 2- bed of activated carbon catalyst layer, water storage tank in 3-, water inlet in 4-, 5- molecular sieve catalyst bed,
Water out in 6-, 7- liquid mixer, 8- go out water storage tank, 9- sodium hypochlorite storage tank, 10- elevator pump, 11- oxidizing tower seal.
Specific embodiment
For a clearer understanding of the technical characteristics, objects and effects of the present invention, this hair of Detailed description of the invention is now compareed
Bright specific embodiment.
A kind of efficient catalytic sodium hypochlorite sewerage disposing system based on composite catalyzing bed of embodiment 1
As shown in Figure 1, the present invention provides a kind of efficient catalytic sodium hypochlorite sewerage disposing system based on composite catalyzing bed
System, including oxidizing tower 1, bed of activated carbon catalyst layer 2, middle water storage tank 3, middle water inlet 4, molecular sieve catalyst bed 5, middle water go out
Mouth 6, goes out water storage tank 8, sodium hypochlorite storage tank 9, elevator pump 10, oxidizing tower seal 11 at liquid mixer 7.
For the middle water storage tank 3 for water in storing, the sodium hypochlorite storage tank 9 is described for storing liquor natrii hypochloritis
Middle water storage tank 3 is connected to liquid mixer 7 by elevator pump 10, and the sodium hypochlorite storage tank 9 is connected to liquid by elevator pump 10 and mixes
Clutch 7, the liquid mixer 7 are connected to the middle water inlet 4 of 1 bottom of oxidizing tower, are provided with activated carbon catalysis in the oxidizing tower 1
Agent bed 2 and molecular sieve catalyst bed 5, the bed of activated carbon catalyst layer 2 are located at the bottom of oxidizing tower 1, the molecular sieve
Catalyst bed 5 is located at the top of bed of activated carbon catalyst layer 2, and the top of the oxidizing tower 1 is provided with middle water out 6, described
Middle water out 6 is connected to out water storage tank 8.Middle water before processing is flowed out by middle water storage tank 3, and liquor natrii hypochloritis is by sodium hypochlorite storage tank
9 flow out, and liquid mixer 7 is mixed and flowed into pipeline after the boosted pump 10 of the middle water and liquor natrii hypochloritis before processing, then
Water inlet 4 enters in oxidizing tower 1 in, by the oxidation catalysis of bed of activated carbon catalyst layer 2 and molecular sieve catalyst bed 5,
Water is flowed into out in water storage tank 8 by middle water out 6 during treated.
Oxidizing tower 1 includes the middle water inlet 4 of bottom connection, the middle water out 6 with tank body top connection.
The oxidizing tower 1 can preferably be dismantled from middle part, and easy to clean and filler loads；More preferably in technical solution,
Oxidizing tower 1 is 316L steel.
In preferred technical solution, liquid-distributing disk is arranged at 1 bottom of oxidizing tower, can push in water uniformly through bed.Instead
Pass through in adjusting depending on the residence time of water between seasonable, mean residence time 3-5h.
Oxidizing tower 1 is pillar oxidizing tower, is highly more than 3:1 with base diameter ratio, 1 bottom of oxidizing tower is provided with middle water and enters
There is apparatus for combining liquids at mouth, middle water inlet, 1 top of oxidizing tower includes middle water out, and the oxidizing tower can be dismantled from middle part, side
Just cleaning and catalyst filling；
Oxidizing tower 1 carries back purge system and hydraulic pressure mensuration metering device, when hydraulic pressure mensuration instrument numerical value is more than day normal pressure
When power numerical value is more, it should be backwashed.
A kind of efficient catalytic sodium hypochlorite mid-water process craft based on composite catalyzing bed of embodiment 2, including following step
It is rapid:
(1) catalyst preparation: the powder of nickel nitrate, ferric nitrate, magnesium nitrate is put into ball mill grinding mixing, will then be mixed
Two parts of aqueous solution that powder is configured to 5% are closed, respectively wherein by molecular sieve and active carbon investment, after soaking 12h, is dried, and
It is calcined afterwards with Muffle furnace, obtains activated-carbon catalyst and molecular sieve catalyst after cooling；
Wherein, nickel nitrate, ferric nitrate, magnesium nitrate mass ratio be 5:2:1；
Molecular sieve selects the molecular sieve of MCM41 type, and the specific surface area of specific molecular sieve is more than 1000m2/ g is opposite to tie
Brilliant degree is more than 90%, and burning decrement is no more than 5%, and aperture is distributed within the scope of 2-5nm.
Active carbon selects coconut husk class active carbon, and specific active carbon mesh number is 12-30 mesh, and intensity is more than 95%, and water content is not
More than 5%, iodine sorption value 1100-1200mg/g, specific surface area 1100-1150m2/g。
The calcination temperature of activated-carbon catalyst is 400-500 DEG C, calcination time 1-3h, more preferably, calcination temperature
It is 450 DEG C, calcination time 2h.The calcination temperature of molecular sieve catalyst is 600-800 DEG C, calcination time 3-5h, more excellent
Choosing, calcination temperature is 700 DEG C, calcination time 4h；
The drying stage is carried out in baking oven, and temperature is 105 DEG C, time 6h.
(2) prepared by catalytic bed: by catalyst preparation step, obtaining activated-carbon catalyst and molecular sieve catalytic after cooling
Agent is successively filled in oxidizing tower with the mass ratio of 1:1, and activated-carbon catalyst is placed in oxidation tower bottom, and molecular sieve catalyst is placed in
Activated-carbon catalyst top, specifically, activated-carbon catalyst is first filled in oxidation tower bottom and is compacted, activated carbon catalysis
Agent bed height accounts for the 15% of oxidizing tower, and then molecular sieve catalyst is filled in oxidizing tower, molecular sieve catalyst bed height
Account for the 15% of oxidizing tower；
Activated-carbon catalyst and molecular sieve catalyst need to load consolidation.
(3) sodium hypochlorite catalysis oxidation: middle water and sodium hypochlorite are mixed in advance, then logical from oxidation tower bottom
Enter, middle water is stopped in oxidizing tower, and centering water carries out catalysis oxidation, the residual organic matter in depth degradation in water；
Liquor natrii hypochloritis's concentration is normally controlled in 1-5%, and sodium hypochlorite is to mix in pipeline with middle water hybrid mode, secondary
The volume ratio of sodium chlorate solution and middle water is 1:200-1000.
Oxidizing tower includes tank body, the middle water out with the middle water inlet of tank base connection and tank body top connection.
The oxidizing tower preferably its tank body can be dismantled from middle part, and easy to clean and filler loads；More preferably technical side
In case, oxidizing tower tank body is 316L steel.
In preferred technical solution, oxidation tower bottom has liquid-distributing disk, can push in water uniformly through bed.Reaction
Depending on residence time of the time by water in adjusting, mean residence time 3-5h.
Oxidizing tower be pillar oxidizing tower, be more than highly 3:1 with base diameter ratio, aoxidize tower bottom be provided with middle water inlet,
There is apparatus for combining liquids at middle water inlet, oxidizing tower top includes middle water out, and the oxidizing tower can be dismantled from middle part, convenient clear
It washes and catalyst filling；
Oxidizing tower carries back purge system and hydraulic pressure mensuration metering device, when hydraulic pressure mensuration instrument numerical value is more than everyday stress
When numerical value is more, it should be backwashed.
(4) water quality indicator measures: the measurement of the indexs such as total organic carbon and total chemical oxygen consumption (COC) is carried out to treated waste water,
Carry out water analysis characterization.
Composite catalyzing bed of the present invention is used for sodium hypochlorite catalysis oxidation water process, due to involved in this patent
Experiment close catalytic bed using same reply and carry out, therefore experimental result it can be proved that composite catalyzing bed except having
It except excellent catalytic activity, also has excellent stability and oxidative resistance, high catalytic activity can be kept for a long time, reduce
React operating cost.
Secondly, the selection of several metallic additions, not only catalytic function is superimposed, and helps to promote catalytic efficiency, Er Qieke
To meet the needs of various wastewater organic matter processing；The combined oxidation bed can guarantee to make several gold in calcination process
Belonging to additive may be uniformly dispersed in active carbon or molecular sieve surface, guarantees interaction of the additive to active site, fills
Divide and improves catalytic effect；In addition, combined oxidation catalytic bed of the present invention, due to mixing specific additive, catalyst
Mechanical strength, hardness and surface anti-pollution be all significantly improved, assign the better application attribute of catalyst.
Secondly, the present invention provides above-mentioned composite catalyzing bed for the application in sodium hypochlorite catalysis oxidation water process.
In preferred technical solution, the application mode of composite catalyzing bed is, respectively by activated-carbon catalyst and molecular sieve
Catalyst is filled in oxidation oxidizing tower, carries out water process.
In preferred technical solution, the application mode of composite catalyzing bed is that activated-carbon catalyst is first filled in oxygen
Change tower bottom and be compacted, bed of activated carbon catalyst layer height accounts for the 15% of oxidizing tower, is then filled in molecular sieve catalyst
In oxidizing tower, molecular sieve catalyst bed height accounts for the 15% of oxidizing tower.Middle water mixed with sodium hypochlorite after from oxidation tower bottom into
Enter.
The invention discloses a kind of efficient catalytic sodium hypochlorite sewerage disposing system and its work based on composite catalyzing bed
Skill, activated-carbon catalyst of the present invention also have excellent stability and resistance to oxidation in addition to excellent catalytic activity
Property, while the case where there is excellent mechanical strength, can be both crushed to avoid activated-carbon catalyst because of bed layer pressure,
It can keep high catalytic activity for a long time again, reduce reaction operating cost；Molecular sieve catalyst of the present invention has excellent
Catalytic activity, the molecular sieve catalyst of more simple nickel-loaded, catalytic activity are significantly increased, while the stability of molecular sieve itself
It is available to be greatly improved, it greatly reduces molecular sieve and is lost because of current scour；Catalyst preparation process of the present invention
It easily realizes that technical process scale is changeable without using extreme condition or difficult purchase reagent, catalyst preparation process, is easy to
Control；Recycled water advanced treatment technique of the present invention all has good COD and TOC for the municipal middle water in more areas and removes
Rate, applicability are wide；Recycled water advanced treatment system of the present invention, operation is simple, and daily maintenance is convenient, and processing cost is low.
A kind of application of the efficient catalytic sodium hypochlorite sewerage disposing based on composite catalyzing bed of embodiment 3
Below according to fact Example the present invention is described in detail, implementation result of the invention is as follows.
1 the second sewage treatment plant of Jinan sewerage disposing of example
1. the powder of nickel nitrate, ferric nitrate, magnesium nitrate (mass ratio 5:2:1) is put into ball mill grinding mixing, then
Mixed-powder is configured to two parts of aqueous solution of 5%, respectively by molecular sieve (molecular sieve of MCM41 type) and active carbon (coconut husk class
Active carbon) it puts into wherein, it after soaking 12h, is dried, is then calcined with Muffle furnace, obtain activated carbon catalysis after cooling
Agent and molecular sieve catalyst.
2. activated-carbon catalyst is first filled in oxidation tower bottom and is compacted, bed of activated carbon catalyst layer height accounts for oxygen
To change the 15% of tower, then molecular sieve catalyst is filled in oxidizing tower, molecular sieve catalyst bed height accounts for the 15% of oxidizing tower,
Form catalyst bed.
3. middle water is therefrom in water storage tank using the second sewage disposal plant effluent of Jinan as recycled water advanced treatment technical study target
It draws after being mixed with the liquor natrii hypochloritis that concentration in sodium hypochlorite storage tank is 3% according to volume ratio 1:500, is led to by middle water inlet
Enter oxidizing tower to be reacted, successively passes through bed of activated carbon catalyst layer and molecular sieve catalyst bed, residence time 3h, water outlet
It is drawn from the middle water out of oxidizing tower, water outlet is stored in out in water storage tank.
4. after the completion of reaction, analyzing the water after reaction, analysis data are shown in Table 1.
Water-quality determination: determining total organic carbon experiment using TOC analyzer (1088 AS of O.I.Analytical Aurora,
The U.S.) it is tested, it by water sample by 0.22 μm of filter membrane, is stored in sample injection bottle, then water sample is carried out using TOC analyzer
Analysis, for global test process using High Purity Nitrogen as carrier gas, TOC analyzer agents useful for same is ultrapure water (milli-Q
The preparation of AdvantageA10 ultrapure water instrument), sodium peroxydisulfate solution (10%, w/w) and phosphoric acid solution (5%, w/w).The measurement of COD is adopted
It is tested with COD tester (HACH DR1000, the U.S.), negates water sample 10mL after answering, screening agent and instruction is successively added
Agent after heated resolution, carries out the measurement of COD numerical value.The specific surface area of catalyst is measured using BET-N2 tester, is surveyed
It is needed before examination by testing tube and 105 DEG C of associated sample dry 6h.
Table 1: water quality indicator before and after the second sewage treatment plant of Jinan sewerage disposing
By above-mentioned table 1 it is found that being 35ppm, TOC value to the middle water COD value before the processing of the second sewage disposal plant effluent of Jinan
For 348ppb, after treatment process of the invention, the COD value of middle water is 10ppm, and TOC value is 27ppb.And two kinds of catalyst
Before and after use, specific surface area is still maintained at previous level without significant change, it was demonstrated that two kinds of catalyst can be maintained for a long time
Catalytic activity.
The municipal middle water of 2 Jining coalfield of example is handled
1. preparation step is the same as example 1.
2. being derived from the municipal middle water of Jining coalfield, processing step is the same as embodiment 1.
3. analytic process is shown in Table 2 with example 1, water analysis data.
Table 2: the municipal middle water of Jining coalfield water quality indicator before and after the processing
By above-mentioned table 2 it is found that being 42ppm, TOC value to the middle water COD value before the processing of Jining coalfield sewage disposal plant effluent
For 336ppb, after treatment process of the invention, the COD value of middle water is 13ppm, and TOC value is 18ppb.And two kinds of catalyst
Before and after use, specific surface area is still maintained at previous level without significant change, it was demonstrated that two kinds of catalyst can be maintained for a long time
Catalytic activity.
The municipal middle water in 3 Weifang Qingzhou area of example is handled
1. preparation step is the same as example 1.
2. being derived from the municipal middle water in Weifang Qingzhou area, processing step is the same as embodiment 1.
3. analytic process is shown in Table 3 with example 1, water analysis data.
Table 3: the municipal middle water in Weifang Qingzhou area water quality indicator before and after the processing
By above-mentioned table 3 it is found that being 48ppm to the middle water COD value before the processing plant effluent processing of Weifang Qingzhou regional waste-water,
TOC value is 442ppb, and after treatment process of the invention, the COD value of middle water is 12ppm, and TOC value is 28ppb.And two kinds are urged
For agent before and after use, specific surface area is still maintained at previous level without significant change, it was demonstrated that two kinds of catalyst can keep longer
The catalytic activity of time.
The municipal middle water of 4 Jinan Area of example is handled
1. preparation step is the same as example 1.
2. being derived from the municipal middle water of Jinan Area, processing step is the same as embodiment 1.Every 3h once supervises effluent quality
It surveys.
3. analytic process is shown in Table 4 with example 1, water analysis data.
Table 4: the municipal middle water of Jinan Area water quality indicator before and after the processing
By above-mentioned table 4 it is found that being 35ppm to the middle water COD value before the processing of Jinan Area municipal middle water, TOC value is
348ppb, after treatment process of the invention, within long period of time, the COD value of middle water can maintain 10-13ppm
Between, TOC value can maintain between 27-36 ppb, and pH value can maintain between 7.66-7.52.To the molecule before sewerage disposing
Sieve catalyst specific surface area is 1200 m2/ g, activated-carbon catalyst specific surface area are 1140 m2/ g, using processing work of the invention
After skill processing, molecular sieve catalyst specific surface area is 1180-1185 m2/ g, activated-carbon catalyst specific surface area 1132-1133
m2/g.The specific surface area of two kinds of catalyst does not have significant change, shows the reactivity of catalyst during the reaction not by shadow
It rings.Prove that the catalytic activity that catalyst can be maintained for a long time, the technique are highly suitable to be applied for recycled water advanced treatment technique
In.
The present invention realizes this using the bed based on modified active carbon catalyst and modified molecular sieve catalyst combination
Catalytic bed effectively reduces the content of hardly degraded organic substance in middle water to the activation of sodium hypochlorite, realizes middle water
Advanced treating.The technique not only greatly improves the utilization efficiency of catalyst, significantly improves the oxidation effectiveness of sodium hypochlorite, and
Catalyst by modified, mechanical strength and surface anti-pollution performance it is equal to effectively improving, avoid catalyst and using
Loss in journey effectively increases the stability of the technique.Therefore the technique has not only fully ensured that the utilization efficiency of catalyst,
So that the catalytic bed can be used for the processing of the municipal middle water in more areas, while extending the service life of catalyst, so that should
The application of technique is greatly improved.The present invention mainly passes through sodium hypochlorite catalysis oxidation of the building based on composite catalyzing bed
Technique realizes the advanced treating to water in more Regional City, realizes and removes to the depth of organic matter in water body, while this is compound
In catalytic bed, two kinds of catalyst pass through metallic ion-doping modification, have excellent stability and mechanical strength, can be with
Effectively reduce loss amount of the catalyst in water treatment procedure.It improves the resistant to pollution performance of catalyst surface simultaneously and chemistry is steady
It is qualitative, the service life of catalyst is improved, catalyst is facilitated to separate with reaction system, improves the reusable of catalyst
Property.Therefore the technique proposes a set of new and effective sodium hypochlorite catalysis oxidation mode, can quickly remove more Regional City
Organic matter in middle water realizes municipal middle water advanced treating, and the technique is expected to be applied to other types of wastewater treatment mistake
Cheng Zhong, therefore the technique has broad application prospects.
The above is the citing of best mode for carrying out the invention, wherein the part that do not address in detail is that this field is common
The common knowledge of technical staff.Protection scope of the present invention is based on the contents of the claims, any based on technology of the invention
The equivalent transformation of enlightenment and progress, also within protection scope of the present invention.
Claims (4)
1. a kind of efficient catalytic sodium hypochlorite mid-water process craft based on composite catalyzing bed, it is characterised in that: including catalysis
Agent preparation step, catalyst includes nickel nitrate, ferric nitrate, magnesium nitrate in the catalyst preparation step；Nickel nitrate, ferric nitrate,
The mass ratio of magnesium nitrate is 5:2:1；
The powder of nickel nitrate, ferric nitrate, magnesium nitrate is put into ball mill grinding mixing, mixed-powder is then configured to 5% water
Two parts of solution, respectively wherein by molecular sieve and active carbon investment, after soaking 12h, 105 DEG C of baking 6h in baking oven is put into, horse is then used
Not furnace is calcined, and obtains activated-carbon catalyst and molecular sieve catalyst after cooling；
The molecular sieve selects the molecular sieve of MCM41 type, and active carbon selects coconut husk class active carbon；
The calcination temperature of the activated-carbon catalyst is 400-500 DEG C, calcination time 1-3h, the calcining temperature of molecular sieve catalyst
Degree is 600-800 DEG C, calcination time 3-5h；
The specific surface area of the molecular sieve is more than 1000 m2/ g, relative crystallinity are more than 90%, and burning decrement is no more than 5%, aperture
It is distributed within the scope of 2-5nm；
The active carbon mesh number is 12-30 mesh, and intensity is more than 95%, and water content is no more than 5%, iodine sorption value 1100-1200mg/
G, specific surface area are 1100-1150 m2/g；
Including catalytic bed preparation step, in the catalytic bed preparation step, by activated-carbon catalyst and molecular sieve catalyst
It is filled into oxidizing tower (1)；The oxidizing tower (1) can dismantle from middle part；Oxidizing tower (1) bottom is equipped with liquid-distributing disk, can
Water is uniformly through bed in promotion；The oxidizing tower (1) be pillar oxidizing tower, the oxidizing tower (1) highly with base diameter ratio
More than 3:1.
2. a kind of efficient catalytic sodium hypochlorite mid-water process craft based on composite catalyzing bed as described in claim 1,
It is characterized in that: activated-carbon catalyst and molecular sieve catalyst being successively filled in oxidizing tower with the mass ratio of 1:1, active carbon is urged
Agent is placed in oxidation tower bottom, and molecular sieve catalyst is placed in activated-carbon catalyst top.
3. a kind of efficient catalytic sodium hypochlorite mid-water process craft based on composite catalyzing bed as described in claim 1,
It is characterized in that: activated-carbon catalyst being first filled in oxidation tower bottom and is compacted, bed of activated carbon catalyst layer height accounts for oxygen
Change the 15% of tower, then molecular sieve catalyst is filled in oxidizing tower, molecular sieve catalyst bed height accounts for the 15% of oxidizing tower；
Activated-carbon catalyst and molecular sieve catalyst need to load consolidation.
4. a kind of efficient catalytic sodium hypochlorite mid-water process craft based on composite catalyzing bed as described in claim 1,
It is characterized in that: including sodium hypochlorite catalytic oxidation stage, middle water and liquor natrii hypochloritis being mixed in advance, then from oxidation
The bottom of tower (1) is passed through, and middle water is stopped in oxidizing tower (1), and mean residence time 3-5h, centering water carries out catalysis oxygen
Change；Liquor natrii hypochloritis's concentration is normally controlled in 1-5%, and liquor natrii hypochloritis is to mix in pipeline with middle water hybrid mode, secondary chlorine
The volume ratio of acid sodium solution and middle water is 1:200-1000.
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