CN105233838B - A kind of O using activated bentonite as carrier3/H2O2Preparation method, catalyst and its application of catalyst - Google Patents
A kind of O using activated bentonite as carrier3/H2O2Preparation method, catalyst and its application of catalyst Download PDFInfo
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- CN105233838B CN105233838B CN201510760538.7A CN201510760538A CN105233838B CN 105233838 B CN105233838 B CN 105233838B CN 201510760538 A CN201510760538 A CN 201510760538A CN 105233838 B CN105233838 B CN 105233838B
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Abstract
The invention provides a kind of O using activated bentonite as carrier3/H2O2The preparation method of catalyst, the catalyst prepared by this method and its application.Using activated bentonite as carrier, after Component Vectors impregnating metal salting liquid, then be supported on another part be not impregnated with carrier by drying roasting obtain catalyst.The catalyst obtained by the inventive method, it is adaptable to be catalyzed O3/H2O2Oxidizing process water process, manufacturing cost, operating cost decrease, and are suitable for large-scale production.
Description
Technical field
The present invention relates to treatment catalyst field, and in particular to a kind of O using activated bentonite as carrier3/H2O2Catalysis
The preparation method of agent, the catalyst prepared by this method and its application.
Background technology
Fenton process (Fenton methods) and Ozonation are the advanced oxidation processes of current industrialization maturation the most, but
Fenton methods are strict to pH requirements, and effluent color dilution increases and can produce substantial amounts of chemical sludge；In Ozonation, the oxygen of ozone
Change ability is not so good as hydroxyl radical free radical, and it is organic small that oxidation product is generally monoaldehyde, dialdehyde, aldehydic acid, monocarboxylic acid, dicarboxylic acids
Molecule, it is difficult to thorough mineralising, although can be by adding Fe3+、Mn2+Strengthen ozone oxidation, but there is also same similar to Fenton methods
The problem of sample.Mainly there are two kinds of approach to improve the oxidability of ozone, one is introducing 3d transition metal ions or will have
The 3d transition metal ions for having catalytic performance is supported on carrier, and oxidability is produced more by the catalysis of 3d transition metal ions
Strong free radical O, OH；The second is being radiated by introducing physical field, mainly there are light, sound, electricity, magnetic etc..
O3/H2O2It is that simple ozonidation is changed into the most economical and most viable approach of advanced oxidation processes, it has
The characteristics of having better than traditional single oxidizing process such as ozone or hydrogen peroxide oxidation process.O3/H2O2Oxidability can be produced very
Strong OH free radicals, its oxidizing potential is 2.80V, compares O3(oxidizing potential 2.07V) and H2O2(oxidizing potential 1.76V) difference
High 35% and more than 59%, oxidability is only second to fluorine.OH free radicals, can be by its direct oxidation to the no selectivity of organic matter
For carbon dioxide, water or mineral salt, new environmental problem is not resulted in.
O3/H2O2Though technique is easily real, O3With H2O2Collaboration produce OH amounts by waste water quality, reaction environment influenceed compared with
Greatly, catalyst, physical field are introduced in system to O3/H2O2It is catalyzed, improves OH yield, and introducing interfacial reaction,
The approach of reaction is added, improving makes its oxidability, be current O so as to reduce Sewage advanced treatment cost3/H2O2Using
The focus of research.
The O of current reported in literature3/H2O2Catalyst is, with metal ion, i.e. catalyst wiring solution-forming, to add in waste water, so
After add O3With H2O2Catalytic reaction is carried out, catalyst is present in the form of ionic state.Although this liquid catalyst can be carried
High O3/H2O2The oxidability of system, but there is catalyst and can not reuse, secondary pollution is easily caused, increase subsequent treatment
The shortcomings of difficulty.If a kind of catalyst of solid can be prepared, make it to O3/H2O2System has preferable catalytic action, in water process
During, these solid catalysts, which are maintained in ozone catalytic reactor, plays catalysed oxidn, it is not necessary to follow-up
Separating measure, will there is its actual application value.
The content of the invention
It is an object of the invention to propose a kind of O using activated bentonite as carrier3/H2O2Catalyst and preparation method thereof.
To reach above-mentioned purpose, the present invention uses following technical scheme.
A kind of O using activated bentonite as carrier3/H2O2The preparation method of catalyst, comprises the following steps：
(1) Bentonite Activation：Acid solution is mixed with bentonite, after 6~8h of stirring reaction under conditions of 50~80 DEG C,
4~5h is stood, is then filtered, washing to neutrality is dried, roasting, grinding 200~250 mesh of sieving obtain activated bentonite；Institute
Acid solution is stated for hydrochloric acid, sulfuric acid or salpeter solution, sour solute is 1 with bentonitic mass ratio:500~1:200；Prepare
Activated bentonite is standby, behind the step of (2) and step (3) use respectively；
(2) prepared by raw material core：Activated bentonite is taken, spherical raw material core is prepared by sugar-coat draft machine；
(3) alta-mud load metal ion：It is another to take activated bentonite, add in metal ion solution and be well mixed, 50
6~8h is stirred under conditions of~80 DEG C, 10~12h is stood, solution is dried or after after solution all volatilization, obtains carried metal
The activated bentonite of ion；The metal ion solution is Mn2+、Fe3+、Al3+、Cu2+Nitrate or sulfate；
(4) after spherical raw material core is mixed with the activated bentonite of loaded metal ion, by sugar-coat draft machine, load is made
The activated bentonite of metal ion is attached to spherical raw material core surface, makes particle diameter continue to increase, obtains catalyst idiosome；Will catalysis
High-temperature roasting after agent idiosome is first dried, obtains described using activated bentonite as the O of carrier3/H2O2Catalyst.
Further, in above-mentioned steps (1), the concentration of acid solution is preferably 5~10mol/L.
Further, in above-mentioned steps (2), the particle diameter of the spherical raw material core prepared is 1~2.5mm.
Further, in above-mentioned steps (3), the mass fraction of the metal ion solution is 5~30%；Activated bentonite
Mass ratio with metal ion solution is 10:1~20:1.
Further, in above-mentioned steps (4), the particle diameter of the catalyst idiosome prepared is 3~8mm.
Further, in above-mentioned steps (1), the temperature of the drying is 150~160 DEG C, the time is 1~2h, the roasting
The temperature of burning is 800~1000 DEG C, the time is 4~5h；In step (4), the temperature of the drying is 150~160 DEG C, the time is
1~2h, the temperature of the roasting is 1000~1200 DEG C, the time is 4~5h.
The present invention is also provided by the above-mentioned catalyst prepared, and the catalyst is in catalysis O3/H2O2Oxidizing process water
Application in processing.
Compared with prior art, the invention has the characteristics that：
The present invention prepares catalyst using activated bentonite as carrier, in view of be carried on inside active component (metal from
Son) it is difficult to effectively be catalyzed O3、H2O2, therefore the catalyst for preparing of the present invention is after Component Vectors impregnating metal salting liquid, then to bear
It is loaded in another part to be not impregnated with carrier, while can so ensureing catalytic performance, saves the usage amount of metal salt.In addition, by
In the active component of catalyst be with the aqueous solution and activated bentonite mixing back loading on original raw material core, due to its material
It is close, therefore its adhesive strength is high, can reduce catalyst loss rate, effectively prevent secondary pollution；Moreover, the haydite prepared is urged
Agent may be reused, and reduce O3/H2O2System running cost, it is easier to realize large-scale industrial production.
Catalyst is by once sintered shaping, and the key of technology is manganese sulfate, aluminum sulfate, ferrous sulfate, ferric sulfate in height
When warm more than 800 DEG C, metal oxide and sulfur dioxide gas are all resolved into, gas is with the tail gas of heating furnace through handling heel row
Put.And the metal oxide being decomposed to form, particle is tiny, is evenly distributed, improves the utilization rate of metal oxide active component,
Also reduce production cost.
This invention can be handled individually water, can be also combined with other method.O3/H2O2By prepared by the present invention urging
After agent catalysis, solid, liquid, gas three-phase oxidation system is formd, interfacial reaction is added, OH yield is improved, can be more
Organic pollutants are effectively removed, its oxidability is significantly improved, and condition of compatibility is more broad, reduces O3、H2O2
Dosage, from another angle save operating cost.
Embodiment
Active component is MnO in the method provided according to present invention, described catalyst2、Al2O3、Fe2O3、
Fe3O4, it is one or more of compound in CuO, the carrier of catalyst is activated bentonite.
Manganese sulfate, cobaltous sulfate, copper sulphate and ferric sulfate aqueous solution mixing bentonite material, the high temperature more than 800 DEG C are made
Under, fine MnO is formed2、Al2O3、Fe2O3、Fe3O4, the particle such as CuO, be evenly distributed in the surface of haydite.Actual production
When, the condition of haydite fire is 1000~1200 DEG C, prepares O3/H2O2Catalyst.The catalyst is carrying out catalytic reaction
When, raising O can be played simultaneously3、H2O2The effect of oxidability, not easily runs off and secondary pollution is caused into waste water again.
O3/H2O2Catalyst is by addition to progress catalysis oxidation organic pollutants in catalyst reaction device.
In water inlet pipe, waste water is mixed into H through pipe-line mixer2O2, while adding O by bottom aerator3, in the lump into catalytic reaction
Device.Catalytic reactor can be divided into downflow type (water flows from the bottom up) and reverse-flow (water flows from top to bottom) according to water (flow) direction
Two kinds, it can be adjusted according to Practical Project.Waste water enters bentonite catalytic filler layer, is being loaded with metal oxide catalyst
Catalytic action under, emerging pollutant is further oxidized.Outlet system loads filter screen and causes the carrier with catalyst not by band
Go out, tail gas absorber collects the ozone remained after reaction, if ozone is not recycled, by ozone tail gas destructor to ozone
Handled, to prevent ozone effusion from polluting.
Embodiment 1
5mol/L salpeter solutions are added in bentonite, nitric acid solute is controlled 1 with bentonitic mass ratio:200；80
Under conditions of DEG C after stirring reaction 6h, 4h is stood, is then filtered, washed to neutrality, 150 DEG C of dry 2h, 800 DEG C of roasting 5h are ground
200 mesh of honed sieve, obtain activated bentonite；Partial activation bentonite is taken, particle diameter is prepared for 2.5mm by sugar-coat draft machine
Spherical raw material core；It is another to take partial activation bentonite, add quantitative Mn (NO3)2、Fe(NO3)3、Al2(SO4)3、Cu(NO3)2Gold
Belong in solion and being well mixed, the mass ratio of four kinds of salt is 2:5:2:1, the mass fraction of metal ion solution is 30%, living
The mass ratio for changing bentonite and metal ion solution is 20:1.6h is stirred under conditions of 80 DEG C, 10h is stood, obtains gold-supported
Belong to the activated bentonite of ion；After spherical raw material core is mixed with the activated bentonite of loaded metal ion, prepared by sugar-coat
Machine, makes the activated bentonite of loaded metal ion be attached to spherical raw material core surface, prepares the catalyst embryo that particle diameter is 8mm
Body, by catalyst idiosome after 160 DEG C dry 1h, in 1000 DEG C of high-temperature roasting 5h, is made the O that activated bentonite is carrier3/
H2O2Catalyst.Utilize catalyst O3/H2O2Oxidation depth handles certain municipal sewage plant after secondary biochemical treatment
Tail water, H2O2、O3Dosage and CODcrMass ratio be H2O2:O3:CODcr=1:2:4, in technique plus catalyst is with adding
The COD of catalystcrRemoval situation is as shown in Table 1.
The sewage treatment plant tail water processing data of one embodiment of table 1
| Number of times | 1 | 2 | 3 | 4 |
| Influent COD (not plus catalyst) | 45 | 52 | 43 | 55 |
| Water outlet COD (not plus catalyst) | 34 | 37 | 34 | 39 |
| COD clearances (not plus catalyst) | 24.44% | 28.85% | 20.93% | 29.09% |
| Influent COD (plus catalyst) | 42 | 48 | 56 | 58 |
| Water outlet COD (plus catalyst) | 26 | 28 | 27 | 26 |
| COD clearances (plus catalyst) | 38.10% | 41.67% | 51.79% | 55.17% |
Independent H2O2/O3COD of the oxidation technology to municipal wastewater tail watercrAverage removal rate is 25.83%, adds bentonite
The heterogeneous catalysis H built after catalyst2O2/O3Oxidation technology, CODcrAverage removal rate is 46.68%, than independent H2O2/O3Technique
Improve 20.85%.In addition to investigating this catalyst to ozone oxidation degradation of organic substances, also to the catalyst surface active component
It is lost in and is analyzed in catalytic oxidation process, the results are shown in Table two.Only copper has very little to this catalyst in catalytic oxidation process
Loss.
Loss of active component data in the catalyst of two embodiment of table 1
Embodiment 2
10mol/L sulfuric acid solutions are added in bentonite, sulfuric acid solute is controlled 1 with bentonitic mass ratio:500；
Under conditions of 50 DEG C after stirring reaction 8h, 5h is stood, is then filtered, washed to neutrality, 160 DEG C of dry 1h, 1000 DEG C of roasting 4h,
Grinding 250 mesh of sieving, obtain activated bentonite；Partial activation bentonite is taken, particle diameter is prepared for 1mm by sugar-coat draft machine
Spherical raw material core；It is another to take partial activation bentonite, add quantitative MnSO4、Fe2(SO4)3、Al2(SO4)3、CuSO4Metal from
It is well mixed in sub- solution, the mass ratio of four kinds of salt is 2:5:2:1, the mass fraction of metal ion solution is 5%, activates swelling
The mass ratio of soil and metal ion solution is 10:1.8h is stirred under conditions of 50 DEG C, 12h is stood, obtains loaded metal ion
Activated bentonite；After mixing spherical raw material core with the activated bentonite of loaded metal ion, by sugar-coat draft machine, make to bear
The activated bentonite of carrying metal ion is attached to spherical raw material core surface, prepares the catalyst idiosome that particle diameter is 3mm, will urge
After 150 DEG C dry 2h, in 1200 DEG C of high-temperature roasting 4h, the O that activated bentonite is carrier is made in agent idiosome3/H2O2Catalysis
Agent.Utilize catalyst O3/H2O2Oxidation depth handles waste water of certain pharmacy waste water after secondary biochemical treatment, H2O2、O3
Dosage and COD mass ratio are H2O2:O3:COD=2:4:5, typical organic matter Diclofenac, carbamazepine, ROX,
Erythromycin degradation rate is respectively 64%, 78%, 73%, 69%, adds catalyst, under same oxidant dosage,
The degradation rate of four kinds of typical organic matters is 87%, 100%, 92%, 86%, has been respectively increased 23%, 22%, 19%, 17%.
In addition to investigating this catalyst to ozone oxidation degradation of organic substances, also to the catalyst surface active component in catalysis
It is lost in and is analyzed in oxidizing process, the results are shown in Table three.Only iron has the loss of very little to this catalyst in catalytic oxidation process.
Loss of active component data in the catalyst of three embodiment of table 2
Claims (8)
1. a kind of O using activated bentonite as carrier3/H2O2The preparation method of catalyst, it is characterised in that comprise the following steps：
(1) Bentonite Activation：Acid solution is mixed with bentonite, after 6~8h of stirring reaction under conditions of 50~80 DEG C, stood
4~5h, is then filtered, washing to neutrality, is dried, roasting, grinding 200~250 mesh of sieving, obtains activated bentonite；The acid
Solution is hydrochloric acid, sulfuric acid or salpeter solution, and sour solute is 1 with bentonitic mass ratio:500~1:200；
(2) prepared by raw material core：Activated bentonite is taken, spherical raw material core is prepared by sugar-coat draft machine；
(3) alta-mud load metal ion：It is another to take activated bentonite, add in metal ion solution and be well mixed, 50~80
6~8h is stirred under conditions of DEG C, 10~12h is stood, obtains the activated bentonite of loaded metal ion；The metal ion solution
For Mn2+、Fe3+、Al3+、Cu2+Nitrate or sulfate；
(4) after spherical raw material core is mixed with the activated bentonite of loaded metal ion, by sugar-coat draft machine, carried metal is made
The activated bentonite of ion is attached to spherical raw material core surface, obtains catalyst idiosome；High temperature after catalyst idiosome is first dried
Roasting, obtains described using activated bentonite as the O of carrier3/H2O2Catalyst.
2. as claimed in claim 1 using activated bentonite as the O of carrier3/H2O2The preparation method of catalyst, it is characterised in that
In step (1), the concentration of the acid solution is 5~10mol/L.
3. as claimed in claim 1 using activated bentonite as the O of carrier3/H2O2The preparation method of catalyst, it is characterised in that
In step (2), the particle diameter of the spherical raw material core prepared is 1~2.5mm.
4. as claimed in claim 1 using activated bentonite as the O of carrier3/H2O2The preparation method of catalyst, it is characterised in that
In step (3), the mass fraction of the metal ion solution is 5~30%；The quality of activated bentonite and metal ion solution
Than for 10:1~20:1.
5. as claimed in claim 1 using activated bentonite as the O of carrier3/H2O2The preparation method of catalyst, it is characterised in that
In step (4), the particle diameter of the catalyst idiosome prepared is 3~8mm.
6. the O using activated bentonite as carrier as described in Claims 1 to 5 is any3/H2O2The preparation method of catalyst, it is special
Levy and be, in step (1), the temperature of the drying is 150~160 DEG C, the time is 1~2h, the temperature of the roasting for 800~
1000 DEG C, the time be 4~5h；In step (4), the temperature of the drying is 150~160 DEG C, the time is 1~2h, the roasting
Temperature be 1000~1200 DEG C, the time be 4~5h.
7. the catalyst that the preparation method as described in claim 1~6 is any is prepared.
8. catalyst as claimed in claim 7 is in catalysis O3/H2O2Application in oxidizing process water process.
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