CN105289610A - Aluminium-oxide-supported iron oxides catalyst, preparation method and application thereof to organic wastewater processing - Google Patents
Aluminium-oxide-supported iron oxides catalyst, preparation method and application thereof to organic wastewater processing Download PDFInfo
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Abstract
The invention discloses a preparation method for an aluminium-oxide-supported iron oxides catalyst, and application of the catalyst to organic wastewater processing. The preparation method comprises the following steps: (1) firstly cleaning an aluminium oxide particle with clean water, and then modifying the aluminium oxide particle by using a low-pressure plasma, so as to obtain modified aluminium oxide; (2) fully dipping the modified aluminium oxide obtained in the step (1) in an iron salt solution, and then drying, so as to obtain iron-loaded aluminium oxide; and (3) calcining the iron-loaded aluminium oxide obtained in the step (2), so as to obtain the aluminium-oxide-supported iron oxides catalyst after calcining is finished. The aluminium-oxide-supported iron oxides catalys obtained by employing the preparation method possesses the advantages of being fast in reaction speed, relatively thorough in organics degradation, high in ozone utilization rate and the like during organic waste water processing.
Description
Technical field
The present invention relates to the method for the ozone oxidation degradation of organic waste water of a kind of low-temperature plasma modified alumina load ferriferous oxide catalyst and institute's catalysis thereof, effectively can remove the organic matter of difficult degradation in waste water, belong to field of waste water treatment.
Background technology
Ozone is a kind of unstable gas with specific stimulation smell, is light blue under normal temperature, liquid lower to navy blue.In conventional oxidant, the oxidability of ozone is very strong, and the standard electrode potential in water is 2.07eV, by oxidation operation easily oxidized in waste water, thus can reach decontamination object; In addition, ozone has stronger corrosivity, and kill bacteria and virus capable by force, are usually used in the exterminating bacterium process of running water and recreational water.
Ozone oxidation is as a kind of traditional water technology, and since 1940 ' s starts, people attempt to use it for sewage disposal, but never extensive implementation.Its reason has: although ozone has very strong oxidisability, generally can not by organic matter exhaustive oxidation, and can only, by its Partial digestion, cause ozone direct oxidation technology to have significant limitation in application.In addition, in ozone direct oxidation process, the utilization rate of ozone is lower, causes a large amount of waste, increases cost.
For the shortcoming of above-mentioned ozone direct oxidation technology, find the more efficient method of one and just become very important.Catalytic ozonation is a kind of new type water treatment technology that developed recently gets up, and those can be difficult to carry out oxidative degradation and even mineralising with the organic matter of ozone direct oxidation or degraded under normal temperature, normal pressure.Its general principle is: the free radical (as hydroxyl radical free radical) that the activity produced in course of reaction is extremely strong, synergy ozone molecule, and by effects such as addition, replacement, electro transfer and scission of links between organic matter, the larger molecular organics of difficult degradation in water is oxidized to low toxicity or nontoxic small-molecule substance, and even exhaustive oxidation becomes CO
2, H
2o and other inorganic matters.Mutually different according to the thing of the catalyst adopted, homogeneous catalysis and heterogeneous catalysis two class catalytic ozonation can be divided into.
In homogeneous catalysis ozone oxidation reaction, catalyst generally adds with the form of soluble metallic salt, and metal ion soluble in water plays catalytic action to ozone oxidation process.Davinson and Hewes studies discovery, in Ozone Water system for handling, adds a certain amount of Fe
2+, Mn
2+, Ni
2+or Co
2+sulfate after, the TOC clearance of waste water is significantly improved.But catalyst is miscible in waste water, very easily causes secondary pollution, and be difficult to be separated, the cost of water treatment increased, is unfavorable for the waste water treatment applications of scale.
For solving the problem, there has been proposed heterogeneous catalysis ozonation technology.Compared with homogeneous catalysis ozonation technology, the main distinction is that solid catalyst provides the activated centre of reaction to ozone oxidation organic matter, and the general load of solid catalyst is here on carrier.Owing to being solid catalyst, be conducive to the permanent use of catalyst, recovery and reuse.The ColinCooper of Britain etc. adopt Fe respectively
2o
3/ Al
2o
3and TiO
2/ Al
2o
3carry out the research (" Aninvestigationofcatalyticozonationfortheoxidationofhalo carbonsindrinkingwaterpreparation " of O3 catalytic oxidation process ethanedioic acid, chlorethanol and chlorophenol, ColinCooper, RobbieBurch, Vol.33, No.18), result shows: load TiO
2and Fe
2o
3al
2o
3catalyst ozone oxidation effect improves a lot than independent ozone oxidation.Meanwhile, being separated also than being easier to of catalyst and waste water.But also there is certain problem in heterogeneous catalysis ozonation technology: (1) catalyst is insecure at supported on carriers; (2) agglomeration of catalyst on carrier is more serious; (3) preenrichment of carrier to pollutant is indifferent.Therefore, the present invention proposes a kind of method of low-temperature plasma modified alumina load ferriferous oxide catalytic ozonation degradation organic wastewater, the above problem existed during to solve catalytic ozonation degradation organic wastewater.
Summary of the invention
The invention provides a kind of preparation method of alumina load ferriferous oxide catalyst and the application in treatment of Organic Wastewater, by adopting low temperature plasma, modification is carried out to alumina support, catalyst is obtained more firm at supported on carriers, decrease the agglomeration of catalyst on carrier, improve the preenrichment ability of carrier to pollutant simultaneously, finally reach the object improving waste water treatment efficiency.
A preparation method for alumina load ferriferous oxide catalyst, comprises the following steps:
(1) first with clear water, alumina particle is cleaned, then adopt low temperature plasma to carry out modification to alumina particle, obtain modified aluminas;
(2) fully flooded in iron salt solutions by the modified aluminas that step (1) obtains, then drying obtains carrying Fe forms aluminium;
(3) step (2) is obtained carry Fe forms aluminium to calcine, after having calcined, obtain described alumina load ferriferous oxide catalyst.
Basic conception of the present invention is exactly adopt low temperature plasma to carry out modification to the aluminium oxide as catalyst carrier.Plasma is the 4th state except solid-state, liquid, gaseous state as material, gas fraction or the non-coacervated system ionizing generation completely, generally comprise free electron, ion, free radical and neutral particle etc., be divided into high-temperature plasma and low temperature plasma according to the difference of temperature.In low temperature plasma, the energy of electronics is up to 1-10eV, and the temperature of other particles only has 300-500K.Electronics accelerates to obtain energy in the electric field, collide with the gas molecule of surrounding, atom, energy just can be transmitted by collision, makes them produce new ion, electronics or makes them become excitation state and very fast rebound ground state again, sending photon and generate free radical.Add alumina material under such circumstances, when plasma and alumina material clash into, the surface that some particles can be injected into material cause collision, scattering, excite, reset, isomery, defect, crystallization and decrystallized, thus change the surface property of material.
Due to the effect of impact of plasma, material surface can produce depression and erosion point, surface roughness is increased, and then the specific area of material and surface reaction site are increased to some extent, there is minimizing to a certain degree in aperture simultaneously, thus is conducive to load and the catalytic reaction of catalyst.BET analysis is carried out to the catalyst of alumina support and preparation, draws the average pore size of different sample and the data of specific area, as shown in table 1.
The aperture of table 1 aluminium oxide and catalyst, specific area
| Sample | Average pore size (nm) | Specific area (m 2/g) |
| Al 2O 3 | 5.2 | 298.1 |
| FeO x/Al 2O 3(roasting) | 9.5 | 128.6 |
| FeO x/Al 2O 3(plasma+roasting) | 6.3 | 183.4 |
As shown in Table 1, the average pore size of aluminium oxide is 5.2nm, and specific area is 298.1m
2/ g.Load FeO
xaluminium oxide after roasting, subsiding appears in endoporus, causes aperture to increase, and the load of active component makes the specific area of catalyst reduce.But, catalyst obtained after plasma modification compared with unmodified catalyst, catalyst Fe O
x/ Al
2o
3(x=0-1.5) specific area significantly increases, aperture reduces, and means that the avtive spot of catalytic reaction increases, enhances the activity of catalyst.
After plasma modification, the surface-active site of alumina support increases, and the dispersive property of catalyst can be made to strengthen.In order to verify that the modification of plasma can make the decentralization of catalyst improve, H is carried out to catalyst
2-TPD measures, and show that data are as shown in table 2.
The H of table 2 catalyst
2desorption rate and decentralization
| Sample | H 2Desorption (μm ol/g) | Decentralization (%) |
| FeO x/Al 2O 3(roasting) | 148.7 | 14.9 |
| FeO x/Al 2O 3(plasma+roasting) | 336.5 | 34.6 |
As can be seen from Table 2, without the alumina load catalyst of plasma modification after roasting, the decentralization of catalyst is 14.9%, and the decentralization through the catalyst of plasma modification alumina load is 34.6%.Therefore draw, after plasma modification, the decentralization of catalyst is greatly improved.
If the energy comparison that the particle of plasma carries is large, the atom of material surface can be scattered and cause defect, and the room of material is increased, and L acid strengthens.Different gas flows can affect kind and the character of the non-equilibrium high energy activation material (excited atom, excited state molecule and free radical etc.) that plasma gas discharge produces, thus produces different effects to the stuctures and properties of catalyst.Such as, under nitrogen flowing, the most oxy radical of material surface can be removed, and pH value is significantly increased, and the process of a few minutes just can make acid material become basic matterial; This of material surface group changes load firmness enhanced activity component greatly.In addition, upper state particle and the material surface effects such as the free radical in plasma, electronics, there is the reactions such as crosslinked by etching and deposition, at material surface polarization group, free radical isoreactivity group, thus realize the hydrophilicity-imparting treatment of material surface.Through the process of 2min, the contact angle of water sharply drops to 39 ° from original 89 °, organic matter can be contacted better with carrier, improve preenrichment ability, accelerate organic degraded.The change of contact angle as shown in Figure 3.
Generally speaking, by plasma modification carrier, not only can increase load capacity and the decentralization of catalyst, catalytic reaction efficiency can be improved simultaneously.Low-temperature plasma modifiedly belong to dry process, meet the requirement of environmental protection; Action time is short, efficiency is high, effective; Modification generally only occurs in top layer (several to hundreds of nanometers), while improving material surface performance, does not change the proper property of matrix; To the process of material, there is universality, the material of shape matching complexity can be processed; Reaction temperature is lower, technique is simple, easy to operate, pollution-free or damage ratio is less.This modification technology has good effect, and more traditional modification technology is significantly improved.
In step (1), clean water mainly in order to wash away the dust in alumina particle hole, makes low temperature plasma act on alumina surface, can change the specific area of aluminium oxide, angle of wetting and surface group.
As preferably, in step (1), the granularity of described alumina particle is 1-10mm.
As preferably, in step (2), the solute of described iron salt solutions is at least one in ferric nitrate, iron chloride, frerrous chloride, ferric sulfate, ferrous sulfate, and mass percent concentration is 1%-10%.
As preferably, in step (2), in step (2), the consumption of maceration extract be the 1.2-2.0 of incipient impregnation liquid doubly, dip time is 1-24h, and impregnating equipment is the one in shaking table, tank diameter.
As preferably, in step (2), dry temperature is 60-110 DEG C, and the dry time is 2-12h, and dry equipment is outstanding one of steaming instrument, baking oven.
As preferably, in step (3), calciner is the one of batch-type furnace, converter, shaft furnace, and calcining heat is 240-650 DEG C, and calcination time is 1-6h.
Present invention also offers a kind of alumina load ferriferous oxide catalyst prepared by described preparation method, comprise catalyst activity component and catalyst carrier, the active component of this catalyst is FeO
x(x=0-1.5), its load capacity is 1-10% (mass percent); The carrier of this catalyst is active γ-Al
2o
3, it is 260-320m than specific area
2/ g.
Present invention also offers a kind of processing method of organic wastewater, comprise the following steps:
Described alumina load ferriferous oxide catalyst is filled in waste water disposal facility, then passing into organic wastewater and ozone makes both on catalyst layer, carry out haptoreaction, organic matter in waste water is by the hydroxyl radical free radical oxidation Decomposition that ozone or ozone decomposed produce under catalyst action, and waste water is processed.
As preferably, described waste water disposal facility is reaction tower or reaction tank, and the loading of catalyst is the 10-60% of waste water disposal facility dischargeable capacity.
Compared with the existing technology, the method has following advantage:
(1) low temperature plasma pretreatment alumina particle, not only can increase the specific area of aluminium oxide, change the acid of alumina surface, basic group simultaneously, thus increase load effect to iron and its oxi, also enhance aluminium oxide as carrier to the preenrichment effect of Organic Pollutants in Wastewater.
(2) low temperature plasma pretreatment alumina particle, changes the angle of wetting of aluminium oxide, thus enhances the wettability of aluminium oxide in waste water, and then improves the preenrichment ability to organic pollution, promotes catalytic oxidation effect.
(3) compared with traditional waste water treatment by ozone oxidation method, the method for this O3 catalytic oxidation process organic wastewater has that reaction rate is fast, organic matter degradation is more thorough, ozone utilization rate advantages of higher.
Accompanying drawing explanation
Fig. 1 is the process chart of catalyst preparing of the present invention;
Fig. 2 is the equipment schematic diagram of wastewater treatment of the present invention;
Fig. 3 is before and after plasma treatment, the change schematic diagram of alumina surface angle of wetting.
Detailed description of the invention
Further instruction is given to technology of the present invention below by specific embodiment.
Embodiment 1
The first step, support modification: get the commercial γ-Al that particle diameter is 1-3mm
2o
3(the prosperous pottery alumina producer of Pingxiang City, γ-Al
2o
3porosity: 0.75) particle 100g, after running water cleaning, 120 DEG C of oven dry.Under the radio-frequency power of the operating pressure of 25Pa, 200W, use Ar+O
2plasma is to activated alumina particle process 3min.
Second step, dipping: above-mentioned modified alumina particle be impregnated in 112.5mL and mass fraction is in the iron nitrate solution of 1%, to shake 12h under the condition of 100r/min in shaking table, then container is put into the outstanding steaming instrument outstanding steaming 12h of 60 DEG C, obtain the particle of load ferric nitrate.
3rd step, roasting: be placed in batch-type furnace by the alumina particle of the load ferric nitrate of drying, at 585 DEG C of roasting temperature 2h, obtains catalyst-year iron activated alumina (FeO
x/ Al
2o
3, x=0-1.5).
The aperture of carrying iron activated alumina catalyst of modification and unmodified (other operations are all identical, only do not comprise the process of plasma treatment), specific area, decentralization, contact angle data are as shown in the table.
Carry iron activated alumina the physical-chemical parameters
| Project | Unmodified | Modification |
| Average pore size (nm) | 10.3 | 9.2 |
| Specific area (m 2/g) | 164.7 | 170.4 |
| Decentralization (%) | 27.5 | 42.6 |
| Contact angle (°) | 95.0 | 40.2 |
Through modification, the average pore size of catalyst decreases, and specific area adds, and the decentralization of catalyst activity component significantly increases, and angle of wetting significantly reduces.
Be filled in reaction column by the catalyst prepared and process phenolic waste water, wastewater flow 1L/h, waste water COD 73mg/L, hydraulic detention time 20min, ozone dosage 25mg/L waste water, runs under room temperature normal pressure.Through heterogeneous catalysis ozone Oxidation Treatment, the COD of phenolic waste water reduces to 55mg/L, and clearance is 24.6%.Under the same terms, with year iron activated alumina of non-modified process for catalyst, heterogeneous catalysis waste water treatment by ozone oxidation under the same terms, COD clearance is 17.4%.
Embodiment 2
The first step, support modification: get the commercial γ-Al that particle diameter is 3-5mm
2o
3(the prosperous pottery alumina producer of Pingxiang City, γ-Al
2o
3porosity: 0.78) particle 3kg, after running water cleaning, 120 DEG C of oven dry.Under the radio-frequency power of the operating pressure of 25Pa, 200W, use N
2plasma is to activated alumina particle process 3min.
Second step, dipping: above-mentioned modified alumina particle be impregnated in 2.808L and mass fraction be 2% ferric nitrate and the solution that mixes by 1:3 of iron chloride in, 12h is stirred with the condition of 500r/min in tank diameter, then baking oven alumina particle being put into 100 DEG C dries 4h, obtains the particle of load ferric nitrate and iron chloride.
3rd step, roasting: have the particle of ferric nitrate and iron chloride to be placed in shaft furnace the load of drying, at 526 DEG C of roasting temperature 1.3h, obtains catalyst-year iron activated alumina (FeO
x/ Al
2o
3x=0-1.5).
The aperture of carrying iron activated alumina catalyst of modification and unmodified (other operations are all identical, only do not comprise the process of plasma treatment), specific area, decentralization, contact angle data are as shown in the table.
Carry iron activated alumina the physical-chemical parameters
| Project | Unmodified | Modification |
| Average pore size (nm) | 10.9 | 9.4 |
| Specific area (m 2/g) | 158.3 | 169.0 |
| Decentralization (%) | 26.8 | 41.4 |
| Contact angle (°) | 97.4 | 41.6 |
Through modification, the average pore size of catalyst decreases, and specific area adds, and the decentralization of catalyst activity component significantly increases, and angle of wetting significantly reduces.
To process the wastewater from chemical industry after biochemical treatment in the Catalyst packing prepared to reactor, wastewater flow is 20L/h, and the COD of waste water is 102mg/L, and hydraulic detention time is 15min, and the dosage of ozone is 40mg/L, runs under normal temperature and pressure.Through heterogeneous catalysis ozone Oxidation Treatment, the COD of industrial wastewater reduces to 70mg/L, and clearance is 31.4%.And under the same terms, with year ironwork Al without plasma treatment
2o
3for catalyst, heterogeneous catalysis ozone Oxidation Treatment industrial wastewater under the same terms, COD clearance is 20.3%.
Embodiment 3
The first step, support modification: get the commercial γ-Al that particle diameter is 1-3mm
2o
3(the prosperous pottery alumina producer of Pingxiang City, γ-Al
2o
3porosity: 0.75) particle 500kg, after running water cleaning, 120 DEG C of oven dry.Under the radio-frequency power of the operating pressure of 25Pa, 50W, use Ar
2+ O
2plasma is to activated alumina particle process 4min.
Second step, dipping: above-mentioned modified alumina particle be impregnated in 562.5L and in the mixed solution that mixes according to the ratio of 1:2:3:1 of ferric nitrate, iron chloride, ferrous nitrate, frerrous chloride that mass concentration is 6%, in tank diameter, be uniformly mixed 12h, then year Fe forms alumina particles put into the baking oven 6h of 95 DEG C.
3rd step, roasting: the alumina particle of ferric nitrate, ferric sulfate, ferrous nitrate and ferrous sulfate mixture is placed in converter by the load of drying, at 465 DEG C of roasting temperature 2.5h, obtains catalyst---carry iron activated alumina (FeO
x/ Al
2o
3, x=0-1.5).
The aperture of carrying iron activated alumina catalyst of modification and unmodified (other operations are all identical, only do not comprise the process of plasma treatment), specific area, decentralization, contact angle data are as shown in the table.
Carry iron activated alumina the physical-chemical parameters
| Project | Unmodified | Modification |
| Average pore size (nm) | 8.9 | 8.0 |
| Specific area (m 2/g) | 176.0 | 189.0 |
| Decentralization (%) | 32.0 | 48.0 |
| Contact angle (DEG C) | 87.4 | 37.4 |
Through modification, the average pore size of catalyst decreases, and specific area adds, and the decentralization of catalyst activity component significantly increases, and angle of wetting significantly reduces.
To process the dyeing waste water after biochemical treatment in the Catalyst packing prepared to reaction tower, wastewater flow is 40m
3/ h, the COD of waste water is 118mg/L, and hydraulic detention time is 25min, and the dosage of ozone is 51mg/L, runs under normal temperature and pressure.Through heterogeneous catalysis ozone Oxidation Treatment, the COD of industrial wastewater reduces to 66mg/L, and clearance is 44.1%.And under the same terms, with year ironwork Al without plasma treatment
2o
3for catalyst, heterogeneous catalysis ozone Oxidation Treatment dyeing waste water under the same terms, COD clearance is 23.8%.
Embodiment 4
The first step, support modification: get the commercial γ-Al that particle diameter is 7-10mm
2o
3(the prosperous pottery alumina producer of Pingxiang City, γ-Al
2o
3porosity: 0.82) particle 50kg, after running water cleaning, 120 DEG C of oven dry.Under the radio-frequency power of the operating pressure of 25Pa, 200W, use Ar+H
2plasma is to activated alumina particle process 3min.
Second step, dipping: above-mentioned modified alumina particle be impregnated in 53.3L and mass concentration be 8% frerrous chloride and the solution that mixes according to the ratio of 1:3 of ferric nitrate in, under normal temperature, 12h is mixed in tank diameter, then put into the baking oven 8h of 105 DEG C, obtain the particle of load iron chloride and ferric nitrate.
3rd step, roasting: the alumina particle of iron chloride and ferric nitrate is placed in shaft furnace by the load of drying, at 603 DEG C of temperature lower calcination 3.1h, obtains catalyst---carry iron activated alumina (FeO
x/ Al
2o
3, x=0-1.5).
The aperture of carrying iron activated alumina catalyst of modification and unmodified (other operations are all identical, only do not comprise the process of plasma treatment), specific area, decentralization, contact angle data are as shown in the table.
Carry iron activated alumina the physical-chemical parameters
| Project | Unmodified | Modification |
| Average pore size (nm) | 9.2 | 8.5 |
| Specific area (m 2/g) | 177.0 | 181.2 |
| Decentralization (%) | 30.4 | 46.9 |
| Contact angle (°) | 88.6 | 39.7 |
Through modification, the average pore size of catalyst decreases, and specific area adds, and the decentralization of catalyst activity component significantly increases, and angle of wetting significantly reduces.
The Catalyst packing prepared is carried out advanced treating to the pharmacy waste water after biochemical treatment in reaction tower, and wastewater flow is 10m
3/ h, the COD of waste water is 65mg/L, and hydraulic detention time is 18min, and the dosage of ozone is 30mg/L, runs under normal temperature and pressure.Through heterogeneous catalysis ozone Oxidation Treatment, the COD of industrial wastewater reduces to 47mg/L, and clearance is 27.7%.And under the same terms, with year iron activated alumina without plasma treatment for catalyst, heterogeneous catalysis ozone Oxidation Treatment pharmacy waste water under the same terms, COD clearance is 19.9%.
Embodiment 5
The first step, support modification: get the commercial γ-Al that particle diameter is 5-7mm
2o
3(the prosperous pottery alumina producer of Pingxiang City, γ-Al
2o
3porosity: 0.803) particle 5kg, after running water cleaning, 120 DEG C of oven dry.Under the radio-frequency power of the operating pressure of 25Pa, 50W, use H
2plasma is to activated alumina particle process 7min.
Second step, dipping: above-mentioned modified alumina particle be impregnated in 5.5L and mass concentration is in the ferric chloride solution of 10%, in tank diameter, mix 12h, the baking oven then putting into 110 DEG C is dried, and obtains the particle of load iron chloride.
3rd step, roasting: the alumina particle of the load iron chloride of drying is placed in batch-type furnace, roasting 5h in 383 DEG C of temperature ranges, obtains catalyst---carry iron activated alumina (FeO
x/ Al
2o
3, x=0-1.5).
The aperture of carrying iron activated alumina catalyst of modification and unmodified (other operations are all identical, only do not comprise the process of plasma treatment), specific area, decentralization, contact angle data are as shown in the table.
Carry iron activated alumina the physical-chemical parameters
| Project | Unmodified | Modification |
| Average pore size (nm) | 9.7 | 8.7 |
| Specific area (m 2/g) | 169.5 | 178.6 |
| Decentralization (%) | 29.2 | 43.8 |
| Contact angle (°) | 89.7 | 42.2 |
Through modification, the average pore size of catalyst decreases, and specific area adds, and the decentralization of catalyst activity component significantly increases, and angle of wetting significantly reduces.
Process phenolic waste water by the Catalyst packing prepared to reaction tower, wastewater flow is 15L/h, and the COD of waste water is 115mg/L, and hydraulic detention time is 31min, and the dosage of ozone is 45mg/L, runs under normal temperature and pressure.Through heterogeneous catalysis ozone Oxidation Treatment, the COD of phenolic waste water reduces to 81mg/L, and clearance is 29.6%.And under the same terms, with year iron activated alumina without plasma treatment for catalyst, heterogeneous catalysis ozone Oxidation Treatment phenolic waste water under the same terms, COD clearance is 20.1%.
Embodiment 6
The first step, support modification: get the commercial γ-Al that particle diameter is 3-5mm
2o
3(the prosperous pottery alumina producer of Pingxiang City, γ-Al
2o
3porosity: 0.78) particle 1t, after running water cleaning, 120 DEG C of oven dry.Under the radio-frequency power of the operating pressure of 25Pa, 50W, use Ar+O
2plasma is to activated alumina particle process 8min.
Second step, dipping: above-mentioned modified alumina particle be impregnated in 1.1m
3and mass concentration be 4% frerrous chloride and the solution that mixes according to the ratio of 1:2 of iron chloride in, under normal temperature, to shake 12h under the condition of 100r/min in shaking table, then container is put into the baking oven 12h of 80 DEG C, obtain the particle of load frerrous chloride and iron chloride mixture.
3rd step, roasting: the load frerrous chloride of drying and the alumina particle of iron chloride mixture are placed in converter, at 377 DEG C of roasting temperature 6.3h, obtain catalyst---carry iron activated alumina (FeO
x/ Al
2o
3, x=0-1.5).
The aperture of carrying iron activated alumina catalyst of modification and unmodified (other operations are all identical, only do not comprise the process of plasma treatment), specific area, decentralization, contact angle data are as shown in the table.
Carry iron activated alumina the physical-chemical parameters
| Project | Unmodified | Modification |
| Average pore size (nm) | 9.8 | 8.1 |
| Specific area (m 2/g) | 166.3 | 175.9 |
| Decentralization (%) | 28.6 | 43.4 |
| Contact angle (°) | 92.3 | 39.8 |
Through modification, the average pore size of catalyst decreases, and specific area adds, and the decentralization of catalyst activity component significantly increases, and angle of wetting significantly reduces.
Filled out in reaction tower by the catalyst prepared and process waste water, wastewater flow is 50m
3/ h, the COD of waste water is 80mg/L, and hydraulic detention time is 23min, and the dosage of ozone is 36mg/L, runs under normal temperature and pressure.Through heterogeneous catalysis ozone Oxidation Treatment, the COD of industrial wastewater reduces to 57mg/L, and clearance is 28.8%.And under the same terms, with year iron activated alumina without plasma treatment for catalyst, under the same terms, heterogeneous catalysis ozone Oxidation Treatment industrial wastewater COD clearance is 17.9%.
Claims (9)
1. a preparation method for alumina load ferriferous oxide catalyst, is characterized in that, comprises the following steps:
(1) first with clear water, alumina particle is cleaned, then adopt low temperature plasma to carry out modification to alumina particle, obtain modified aluminas;
(2) fully flooded in iron salt solutions by the modified aluminas that step (1) obtains, then drying obtains carrying Fe forms aluminium;
(3) step (2) is obtained carry Fe forms aluminium to calcine, after having calcined, obtain described alumina load ferriferous oxide catalyst.
2. the preparation method of alumina load ferriferous oxide catalyst according to claim 1, is characterized in that, in step (1), the granularity of described alumina particle is 1-10mm.
3. the preparation method of alumina load ferriferous oxide catalyst according to claim 1, it is characterized in that, in step (2), the solute of described iron salt solutions is at least one in ferric nitrate, iron chloride, frerrous chloride, ferric sulfate, ferrous sulfate, and mass percent concentration is 1%-10%.
4. the preparation method of alumina load ferriferous oxide catalyst according to claim 1, it is characterized in that, in step (2), the consumption of maceration extract is 1.2-2.0 times of incipient impregnation liquid, dip time is 1-24h, and impregnating equipment is shaking table or tank diameter.
5. the preparation method of alumina load ferriferous oxide catalyst according to claim 1, is characterized in that, in step (2), dry temperature is 60-110 DEG C, and the dry time is 2-12h, and dry equipment steams instrument or baking oven for outstanding.
6. the preparation method of alumina load ferriferous oxide catalyst according to claim 1, it is characterized in that, in step (3), calciner is the one in van-type stove, converter, shaft furnace, calcining heat is 240-650 DEG C, and calcination time is 1-6h.
7. the alumina load ferriferous oxide catalyst prepared by the preparation method described in any one of claim 1-6, is characterized in that, according to mass percent, the content of active component is 1%-10%, and the content of alumina support is 90%-99%.
8. a processing method for organic wastewater, is characterized in that, comprises the following steps:
Alumina load ferriferous oxide catalyst according to claim 7 is filled in waste water disposal facility, then passing into organic wastewater and ozone makes both on catalyst layer, carry out haptoreaction, organic matter in waste water by the hydroxyl radical free radical oxidation Decomposition that ozone or ozone decomposed produce, obtains the waste water after processing under catalyst action.
9. the processing method of organic wastewater according to claim 8, is characterized in that, described waste water disposal facility is reaction tower or reaction tank, and the loading of catalyst is the 10-60% of waste water disposal facility dischargeable capacity.
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| CN108686673A (en) * | 2018-05-17 | 2018-10-23 | 万华化学集团股份有限公司 | A kind of ozone catalytic oxidation catalyst and preparation method thereof |
| CN109718803A (en) * | 2018-06-29 | 2019-05-07 | 光大水务（深圳）有限公司 | A kind of catalyst and its preparation, application method for handling waste water nbsCOD |
| CN110152639A (en) * | 2019-06-19 | 2019-08-23 | 渤海大学 | The preparation method of modified aluminium oxide supports and the preparation method and application of supported bi-metallic oxide catalyst |
| CN110639491A (en) * | 2018-06-26 | 2020-01-03 | 宁波市雨辰环保科技有限公司 | Catalyst for harmless treatment of highly toxic wastewater and preparation method and application thereof |
| CN111229225A (en) * | 2020-03-25 | 2020-06-05 | 杭州英普环境技术股份有限公司 | Iron composite catalyst for ozone catalytic oxidation and preparation method thereof |
| CN112408578A (en) * | 2020-11-26 | 2021-02-26 | 上海绿强新材料有限公司 | Catalytic ozone oxidation honeycomb filler and preparation and printing and dyeing wastewater advanced treatment method |
| CN112516954A (en) * | 2020-11-27 | 2021-03-19 | 常熟理工学院 | Method for preparing nano aluminum-based adsorption material by using aluminum slag |
| CN113042052A (en) * | 2021-03-30 | 2021-06-29 | 中建三局绿色产业投资有限公司 | TiO2Al/Si-C-based porous core-shell separation spherical catalyst and preparation method and application thereof |
| CN113101940A (en) * | 2021-04-25 | 2021-07-13 | 山西中科国蕴环保科技有限公司 | Catalyst for activating persulfate and method for treating sewage by using catalyst |
| CN117427685A (en) * | 2023-12-20 | 2024-01-23 | 山东寿光鲁清石化有限公司 | Reforming method of naphtha |
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| CN108686673A (en) * | 2018-05-17 | 2018-10-23 | 万华化学集团股份有限公司 | A kind of ozone catalytic oxidation catalyst and preparation method thereof |
| CN108686673B (en) * | 2018-05-17 | 2021-07-23 | 万华化学集团股份有限公司 | Ozone catalytic oxidation catalyst and preparation method thereof |
| CN110639491A (en) * | 2018-06-26 | 2020-01-03 | 宁波市雨辰环保科技有限公司 | Catalyst for harmless treatment of highly toxic wastewater and preparation method and application thereof |
| CN110639491B (en) * | 2018-06-26 | 2022-09-16 | 宁波市雨辰环保科技有限公司 | Catalyst for harmless treatment of highly toxic wastewater and preparation method and application thereof |
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| CN110152639A (en) * | 2019-06-19 | 2019-08-23 | 渤海大学 | The preparation method of modified aluminium oxide supports and the preparation method and application of supported bi-metallic oxide catalyst |
| CN110152639B (en) * | 2019-06-19 | 2022-11-04 | 渤海大学 | Preparation method of modified alumina carrier, preparation method and application of supported bimetallic oxide catalyst |
| CN111229225A (en) * | 2020-03-25 | 2020-06-05 | 杭州英普环境技术股份有限公司 | Iron composite catalyst for ozone catalytic oxidation and preparation method thereof |
| CN112408578A (en) * | 2020-11-26 | 2021-02-26 | 上海绿强新材料有限公司 | Catalytic ozone oxidation honeycomb filler and preparation and printing and dyeing wastewater advanced treatment method |
| CN112516954A (en) * | 2020-11-27 | 2021-03-19 | 常熟理工学院 | Method for preparing nano aluminum-based adsorption material by using aluminum slag |
| CN112516954B (en) * | 2020-11-27 | 2023-04-21 | 常熟理工学院 | Method for preparing nano aluminum-based adsorption material by utilizing aluminum slag |
| CN113042052A (en) * | 2021-03-30 | 2021-06-29 | 中建三局绿色产业投资有限公司 | TiO2Al/Si-C-based porous core-shell separation spherical catalyst and preparation method and application thereof |
| CN113042052B (en) * | 2021-03-30 | 2022-04-29 | 中建三局绿色产业投资有限公司 | TiO2Al/Si-C-based porous core-shell separation spherical catalyst and preparation method and application thereof |
| CN113101940A (en) * | 2021-04-25 | 2021-07-13 | 山西中科国蕴环保科技有限公司 | Catalyst for activating persulfate and method for treating sewage by using catalyst |
| CN117427685A (en) * | 2023-12-20 | 2024-01-23 | 山东寿光鲁清石化有限公司 | Reforming method of naphtha |
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