CN107051491A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107051491A CN107051491A CN201710275023.7A CN201710275023A CN107051491A CN 107051491 A CN107051491 A CN 107051491A CN 201710275023 A CN201710275023 A CN 201710275023A CN 107051491 A CN107051491 A CN 107051491A
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- solid catalyst
- iii
- ozone heterogeneous
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Abstract
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and technical field of chemical engineering catalysts.With perlite, albite, bentonite, polyhalite, potassium feldspar and boromagnesite make carrier after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant nonyl phenolic group bi-quaternary ammonium salt and activation process is carried out under ul-trasonic irradiation, then carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor 1, 1, 1 trifluoroacetylacetone (TFA) neodymium, three (6, 6, 7, 7, 8, 8, 8 seven fluorine 2, 2 dimethyl 3, 5 octene diketone) dysprosium (III), ten water holmium oxalates, trifluoromethayl sulfonic acid thulium (III), catalytic active center predecessor cobalt edetate, citric acid nickel, ethylenediamine pyrocatechol tungsten complex and the ammino platinum of dichloro two, hydro-thermal reaction is carried out under the effect of emulsifying agent laurate dimethylamino-ethanol ester ammonium chloroacetate, drying is removed after moisture, calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application；Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low；Activated centre is universal
Using normal transition metal salt, mithridatism is poor；Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
The adsorptivity of catalyst, catalytic activity auxiliary agent predecessor, normal transition Organometallic are made using Rare-earth chemicals
Compound and precious metal chemical complex are made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering
Ozone Heterogeneous oxidation solid catalyst containing multi-element metal has to improve the preparation method of catalyst mithridatism and catalytic activity
There are larger environmental benefit and higher practical value.
The content of the invention
For existing in current ozone Heterogeneous oxidation solid catalyst preparation method, Catalyst Adsorption is relatively low, mithridatism
Poor to lose catalytic activity problem with easy, exploitation strengthens catalyst using multicomponent porous carrier through reaming, surface active
Adsorptivity, catalytic activity auxiliary agent predecessor, normal transition metallo-organic compound and expensive are made using Rare-earth chemicals
Metallic compound is made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering containing polynary gold
The ozone Heterogeneous oxidation solid catalyst of category to improve the preparation method of catalyst mithridatism and catalytic activity, it is characterized in that
Component A can be added in closed reactor and deionized water stirring prepares the aqueous solution, the weight concentration for control component A is 2%~6%,
After the completion of prepared by solution, B component is added under agitation, 35 DEG C~50 DEG C are warming up to, continues stirring reaction 3h~6h, is filtered, instead
Product is answered to obtain reaming modified support after 102 DEG C~106 DEG C dry constant weights；Reaming modified support puts into ultrasound reactor,
The aqueous solution prepared by component C and deionized water is added, the weight concentration of component C is 3%~8%, is uniformly mixed, and control is super
Sound power density is 0.3~0.8W/m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasound
Surface active carrier mixed liquor；Ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, add D components and go from
The aqueous solution that sub- water is prepared, the weight concentration of D components is 40%~55%, by weight, D component deionized water solutions:Ultrasonic table
Weight ratio=1 of face activated carrier mixed liquor:（1.5~2）, control 120 DEG C~180 DEG C of temperature, the hydro-thermal reaction time be 8h~
16h, then dries to obtain fine particle；Fine particle is in Muffle furnace, 600 DEG C~950 DEG C, and calcination 3h~8h obtains ozone non-
Homogeneous oxidizing solid catalyst.The component A is made up of lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, by weight, lithium hypochlorite:
Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component is long by perlite, albite, bentonite, polyhalite, potassium
Stone, boromagnesite composition, by weight, perlite:Albite:Bentonite:Polyhalite:Potassium feldspar:The weight ratio of boromagnesite=
（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight of B component
The ratio between=1:（10~20）, component C is nonyl phenolic group bi-quaternary ammonium salt, by weight, component C:The weight ratio of reaming modified support
=1:（5~10）, D components are by composite mineralizer borax, potassium sulfate, the trifluoroacetylacetone (TFA) of catalytic activity auxiliary agent predecessor 1,1,1-
Neodymium, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III), ten water holmium oxalates, fluoroform
Sulfonic acid thulium (III) Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound glucose
Sour cobalt, citric acid nickel, ethylenediamine pyrocatechol tungsten complex and the ammino platinum of precious metal chemical complex dichloro two, emulsifying agent laurate two
Methyl aminoethanol ester ammonium chloroacetate is constituted, by weight, borax:Potassium sulfate:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three (6,6,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 7,8,8,8- seven) dysprosium (III):Ten water holmium oxalates:Trifluoromethayl sulfonic acid thulium (III):
Cobalt edetate:Citric acid nickel:Ethylenediamine pyrocatechol tungsten complex:The ammino platinum of dichloro two:Laurate dimethylamino-ethanol ester
The weight ratio of ammonium chloroacetate=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~
18）:（4~7）:（6~9）:（6~20）.Perlite, albite, bentonite, polyhalite, potassium feldspar, the boron magnesium of the B component
Stone is crushed respectively, and deionized water washing, which is dried, to be removed after moisture, and -200 mesh ,+400 mesh sieves point, control are carried out through standard screen
Particle diameter is the mm of 0.0370mm~0.0750.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Perlite, albite, bentonite, polyhalite, potassium feldspar and boromagnesite porous material carrier, in certain temperature and stirring condition
Under, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material big
Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increase,
Filtering, dries the reaming modified support input ultrasound reactor after constant weight, adds nonyl phenolic group bi-quaternary ammonium salt [(C2H5)2NCH2C6H2(OH)(C6H19)CH2N(C2H5)3]2 +Br2 -The aqueous solution, controls ultrasonic power density, ultrasonic frequency, temperature and surpasses
The sound oscillation time, under ultrasonic cavitation effect, nonyl phenolic group bi-quaternary ammonium salt [(C2H5)2NCH2C6H2(OH)(C6H19)CH2N
(C2H5)3]2 +Br2 - It is easy to escape into reaming modified support duct from the aqueous solution or is attached to reaming modified support surface, it is beneficial
In being interconnected and carrier surface activation for carrier duct, adsorptivity is enhanced；After the completion of ultrasonic activation, ultrasonic surface activation is carried
Body mixed liquor is transferred in hydrothermal reaction kettle, with borax Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, catalytic activity
Auxiliary agent predecessor 1,1,1- trifluoroacetylacetone (TFA) neodymiums C15H12F9NdO6, three (fluoro- 2,2- dimethyl -3 of 6,6,7,7,8,8,8- seven,
5- octenes diketone) dysprosium (III) C30H30DyF21O6, ten water holmium oxalate C6Ho2O12, trifluoromethayl sulfonic acid thulium (III)
C3F9O9S3Tm Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound grape
Saccharic acid cobalt C12H22O14Co, citric acid nickel C12H10O14Ni3, ethylenediamine pyrocatechol tungsten complex (NH2 CH2CH2NH3)2[W(VI)
O2(OC6H4O)2] and the ammino platinum Pt (NH of dichloro two3)2Cl2Precious metal chemical complex, in emulsifying agent laurate dimethylamino-ethanol ester
Ammonium chloroacetate C11H23COOCH2CH2N+(CH3)2Cl-CHCOOH effects are lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, made
Reactant lattice is activated, and promotes the progress of solid phase reaction, ultrasonic surface activated carrier and Rare-earth chemicals, common
Transition metal organometallic compound, precious metal chemical complex Uniform Doped, emulsifying agent laurate dimethylamino-ethanol ester ammonium chloroacetate make
Reaction solution forms quasi-stationary emulsion and prevents separation of solid and liquid, sedimentation, while to the further surface active of porous carrier, by
Certain temperature, the hydro-thermal reaction of time, drying obtain the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped is in Muffle furnace
Interior, through high temperature sintering, organic matter carbonization therein further enhances the microcellular structure of porous carrier, obtains porous carrier
The ozone Heterogeneous oxidation of the catalytic active center of supported rare earth metal oxide, transition metal oxide and noble metal formation is consolidated
Body catalyst, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is that perlite, albite, swelling are used in technology of preparing
Soil, polyhalite, potassium feldspar, boromagnesite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, nonyl phenolic group bi-quaternary ammonium salt [(C2H5)2NCH2C6H2(OH)(C6H19)CH2N(C2H5)3]2 +Br2 -、
Laurate dimethylamino-ethanol ester ammonium chloroacetate C11H23COOCH2CH2N+(CH3)2Cl-CHCOOH is interconnected and table to duct
Face activation；Rare-earth chemicals, normal transition metallo-organic compound and noble metal are made by hydro-thermal reaction
Compound reaches Uniform Doped and is attached in carrier surface and duct that high temperature sintering makes organic matter carbonization strengthen and form
Multi-level microcellular structure, it is polynary that porous carrier supported rare earth metal oxide, transition metal oxide and noble metal are formed
Metal catalytic activity center is combined more firm with porous carrier, and the ozone Heterogeneous oxidation solid catalyst of preparation has stronger
Adsorptivity, the cooperative effect of multi-element metal, particularly doping noble metal there is stability and high activity, metal can be suppressed
Liquating out for catalytic active component, improves the mithridatism and catalytic activity of catalyst, with good environmental benefit and economy
Benefit.
Embodiment
Embodiment 1:1.35g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.65g, 140ml deionized waters are added to volume for 500ml
Can be uniformly mixed in closed reactor, the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (acetylacetone,2,4-pentanedione) berylliums
Weight ratio=1:1.2；Add deionized water wash to it is neutral, 103 DEG C dry and remove the mesh of -200 mesh of sieving after moisture~+400
2.75g perlites, 3.75g albites, 4.75g bentonites, 5.75g polyhalites, 6.75g potassium feldspars, the 7.75g boron magnesium of standard screen
The weight of stone, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3g）:The weight of porous material（31.5g）=1:10.5, it is warming up to 36
DEG C, obtain reaming modified support 31g after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；In 500ml ultrasonic responses
In device, reaming modified support 31g is put into, 3.25g nonyl phenolic group bi-quaternary ammonium salts is added and is dissolved in the water-soluble of 100ml deionized waters
Liquid, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, nonyl phenolic group bi-quaternary ammonium salt（3.25g）:Reaming modified support
（31g ）=1:9.5；It is 0.4 W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, 41 DEG C of temperature, sonic oscillation
2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 500ml hydro-thermals anti-
Answer in kettle, add by 2.1g boraxs, 3.05g potassium sulfates, 1.6g1,1,1- trifluoroacetylacetone (TFA) neodymium, 2.05g tri- (6,6,7,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 8,8,8- seven) dysprosium (III), the water holmium oxalates of 2.6g ten, 3.05g trifluoromethayl sulfonic acids
Thulium (III), 5.05g cobalt edetates, 6.1g citric acids nickel, 2.05g ethylenediamine pyrocatechols tungsten complex, 3.1g dichloros two
The aqueous solution that ammino platinum, 3.05g laurate dimethylamino-ethanol ester ammonium chloroacetate and 50ml deionized waters are prepared, the aqueous solution
Weight concentration be 40.3%, the weight of the aqueous solution:Weight=83.8g of ultrasonic surface activated carrier mixed liquor:134.25g =
1:1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then dries to obtain fine silt thing for 105 DEG C；Fine silt thing is in Muffle
In stove, 620 DEG C, calcination 3.2h after cooling down, can obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 1.45g perlites of 400 mesh standard sieves, 1.65g albites, 1.85g bentonites, 2.05g polyhalites, 2.25g potassium feldspars,
The weight of 2.45g boromagnesites, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（0.6g）:The weight of porous material（11.7g）=1:
19.5,48 DEG C are warming up to, reaming modified support 11.5g is obtained after continuing stirring reaction 5.8h, filtering, 105 DEG C of dry constant weights；
In 100ml ultrasound reactors, reaming modified support 11.5g is put into, 2.2g nonyl phenolic group bi-quaternary ammonium salts is added and is dissolved in 26ml
The aqueous solution of deionized water, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, nonyl phenolic group bi-quaternary ammonium salt
（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7 W/m to control ultrasonic power density3, ultrasonic frequency 29kHz,
54 DEG C of temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor
It is transferred in 100ml hydrothermal reaction kettles, adds by 0.78g boraxs, 0.97g potassium sulfates, 0.58g1,1,1- trifluoroacetylacetone (TFA)
Neodymium, 0.67g tri- (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosium (III), the pasture and water of 0.78g ten acid
Holmium, 0.87g trifluoromethayl sulfonic acids thulium (III), 1.48g cobalt edetates, 1.77g citric acids nickel, 0.68g catechols second two
Amine tungsten complex, the ammino platinum of 0.87g dichloros two, 1.98g laurate dimethylamino-ethanol ester ammonium chloroacetate and 10ml deionized waters
The aqueous solution of preparation, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasonic surface activated carrier mixed liquor
Weight=21.43g:39.7g =1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, is then dried for 105 DEG C
Fine silt thing；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, can obtain the ozone of fine particle shape
Heterogeneous oxidation solid catalyst.
Comparative example 1:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, nonyl phenolic group bi-quaternary ammonium salt, laurate
Outside dimethylamino-ethanol ester ammonium chloroacetate, borax and potassium sulfate, whole preparation process, preparation condition are identical with embodiment 1.
The parameter of ozone Heterogeneous oxidation solid catalyst prepared by embodiment 1, embodiment 2 and comparative example 1 is included in table 1.
The embodiment of table 1 and comparative example prepare ozone Heterogeneous oxidation solid catalysis agent parameter
| Project | Average pore size (nm) | Pore volume (cm3/g) | BET is than surface (m2/g) |
| Embodiment 1 | 4.609 | 0.6113 | 779.21 |
| Embodiment 2 | 4.005 | 0.5511 | 698.97 |
| Comparative example 1 | 2.012 | 0.3013 | 498.02 |
Claims (2)
1. a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, it is characterized in that A groups can added in closed reactor
Divide and deionized water stirring prepares the aqueous solution, the weight concentration for controlling component A is 2%~6%, after the completion of prepared by solution, in stirring
Lower addition B component, is warming up to 35 DEG C~50 DEG C, continues stirring reaction 3h~6h, and filtering, reaction product is dry at 102 DEG C~106 DEG C
Reaming modified support is obtained after dry constant weight, reaming modified support input ultrasound reactor, addition is matched somebody with somebody by component C and deionized water
The aqueous solution of system, the weight concentration of component C is 3%~8%, is uniformly mixed, and it is 0.3~0.8W/ to control ultrasonic power density
m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasonic surface activated carrier mixed liquor, transfer
Into hydrothermal reaction kettle, the aqueous solution that D components and deionized water are prepared is added, the weight concentration of D components is 40%~55%, is pressed
Weight meter, D component deionized water solutions:Weight ratio=1 of ultrasonic surface activated carrier mixed liquor:（1.5~2）, control temperature
120 DEG C~180 DEG C, the hydro-thermal reaction time is 8h~16h, then dries to obtain fine silt thing, fine silt thing is in Muffle furnace, 600
DEG C~950 DEG C, calcination 3h~8h obtains ozone Heterogeneous oxidation solid catalyst；The component A by expanding agent lithium hypochlorite,
Double (acetylacetone,2,4-pentanedione) beryllium compositions, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B groups
Divide and be made up of perlite, albite, bentonite, polyhalite, potassium feldspar, boromagnesite, by weight, perlite:Albite:Swelling
Soil:Polyhalite:Potassium feldspar:The weight ratio of boromagnesite=（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:
（15~25）, by weight, component A:Weight ratio=1 of B component:（10~20）, component C is nonyl phenolic group bi-quaternary ammonium salt, is pressed
Weight meter, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are urged by composite mineralizer borax, potassium sulfate
Change coagent predecessor 1,1,1- trifluoroacetylacetone (TFA)s neodymiums, three (the fluoro- 2,2- dimethyl -3,5- of 6,6,7,7,8,8,8- seven are pungent
Alkene diketone) dysprosium (III), ten water holmium oxalates, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center predecessor is general
Logical transition metal organometallic compound cobalt edetate, citric acid nickel, ethylenediamine pyrocatechol tungsten complex and precious metal chemical complex
The ammino platinum of dichloro two, emulsifying agent laurate dimethylamino-ethanol ester ammonium chloroacetate composition, by weight, borax:Potassium sulfate:1,1,
1- trifluoroacetylacetone (TFA) neodymiums:Three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III):Trifluoro
Loprazolam thulium (III):Carbonic acid lutetium hydrate:Cobalt edetate:Citric acid nickel:Ethylenediamine pyrocatechol tungsten complex:Dichloro
Two ammino platinum:The weight ratio of laurate dimethylamino-ethanol ester ammonium chloroacetate=（4~8）:（6~10）:（3~6）:（4~7）:
（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.
2. B component is made up of perlite, albite, bentonite, polyhalite, potassium feldspar, boromagnesite according to claim 1,
Perlite, albite, bentonite, polyhalite, potassium feldspar, boromagnesite are crushed respectively, and deionized water washing, which is dried, removes water
After point, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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