CN102626639A - Catalyst for microwave degradation of printing and dyeing wastewater and preparation method thereof - Google Patents
Catalyst for microwave degradation of printing and dyeing wastewater and preparation method thereof Download PDFInfo
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- CN102626639A CN102626639A CN2012100759450A CN201210075945A CN102626639A CN 102626639 A CN102626639 A CN 102626639A CN 2012100759450 A CN2012100759450 A CN 2012100759450A CN 201210075945 A CN201210075945 A CN 201210075945A CN 102626639 A CN102626639 A CN 102626639A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000002351 wastewater Substances 0.000 title claims abstract description 25
- 238000004043 dyeing Methods 0.000 title claims abstract description 16
- 230000015556 catabolic process Effects 0.000 title claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 238000007605 air drying Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- PWBYYTXZCUZPRD-UHFFFAOYSA-N iron platinum Chemical compound [Fe][Pt][Pt] PWBYYTXZCUZPRD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention relates to a catalyst for microwave degradation of printing and dyeing wastewater and a preparation method thereof. The catalyst takes active alumina as a carrier, rare earth metal as a cocatalyst component, and noble metal and transition metal as active components; wherein the mass ratio of the carrier to the rare earth metal oxide, the noble metal and the transition metal oxide is 100 to (0.2-2.5) to (0.1-0.5) to (0.3-3.5). And (3) dipping the pretreated carrier in a rare earth metal salt solution, a noble metal salt solution and a soluble transition metal salt solution, naturally air-drying, carrying out heat treatment and roasting to obtain the composite metal catalyst. The catalyst prepared by the invention has high mechanical strength, the preparation method is simple and easy to implement, the operation is convenient, the catalyst is suitable for catalytic oxidation under the microwave condition, the catalytic oxidation reaction rate can be improved, the chromaticity of printing and dyeing wastewater can be quickly reduced, and the biodegradability of the wastewater can be improved.
Description
Technical field
The present invention relates to the sewage disposal catalyst preparation technical field, particularly relate to a kind of Catalysts and its preparation method that is used for the microwave degradation dyeing waste water.
Background technology
Along with the fast development of industry, emerge numerous method for treating water.Characteristics such as wherein high-level oxidation technology is wide with its scope of application, treatment effeciency is high, reaction speed is fast, secondary pollution is few have received the favor of Chinese scholars.Since microwave have heating efficient fast, can carry out the selectivity heating, be convenient to control, equipment volume is little and characteristic such as no waste generation, is applied to the aspects such as development and environmental monitoring of processing and the environment-friendly materials of waste water, waste gas, solid waste gradually.
The microwave catalysis oxidation technology is as a kind of wastewater treatment new method that grows up; Utilize the heating of microwave energy selectivity; Can make magnetisable material produce " focus ", reduce reaction activity, quicken the removal of pollutant, transitory efficient; Especially better to unmanageable organic pollution effect, become the focus of studying in the nearest high-level oxidation technology.Catalyst is as the core of catalytic oxidation, and research and development are applicable to that the effective catalyst of microwave catalysis system is the key that improves and expand the microwave catalysis oxidation technology.
Simultaneously, for improving the degradation rate and the microwave utilization rate of pollutant in the waste water, make catalyst absorb microwave energy in a large number, the material of selecting ability strong absorption microwave is the key factor that improves contaminant degradation as catalytic component.In addition, reduce loss of active component, improving catalyst mechanical strength and utilization rate also is the problem that needs attention.
At present, Zhang Jinsheng adopts active carbon as the mass treatment oily waste water that absorbs radiation, but the mechanical strength of active carbon is not high, under microwave action, is prone to produce sintering; Though Chinese patent CN101073773A nm-class catalyst good dispersion property, also existing with the carbon source is carrier, the deficiency that nano material is difficult for Separation and Recovery, can not recycles.Chinese patent CN1765494A adopts that soluble-salt solution is compound with the gelatin polymer part with network structure, the pyrolysis calcining obtains composite foam shape catalyst, and preparation technology is complicated, and energy consumption and cost are higher.
Summary of the invention
The objective of the invention is to improve the deficiency of prior art and a kind of catalyst that is used for the microwave degradation dyeing waste water is provided, another object of the present invention provides above-mentioned Preparation of catalysts method.
Technical scheme of the present invention is: a kind of catalyst that is used for the microwave degradation dyeing waste water, it is characterized in that with the activated alumina being carrier, and rare earth metal is for helping catalyst component, and noble metal and transition metal are as active component; Wherein the carrier quality is 100 with the mass ratio of the rare-earth oxide, noble metal and the transition metal oxide that support: (0.2-2.5): (0.1-0.5): (0.3-3.5).
The present invention also provides above-mentioned Preparation of catalysts method, and its concrete steps are following:
(1) with for use after the carrier preliminary treatment; Described carrier is an activated alumina;
(2) carrier impregnation after the preliminary treatment is gone into rare earth metal salt solutions, roasting in Muffle furnace after mixing, the natural air drying heat treatment;
(3) with the carrier impregnation after the roasting in the step (2) in precious metal salt solution, natural air drying after-baking behind the mixing, the presoma of carried noble metal;
(4) presoma with step (3) carried noble metal places nitrogen atmosphere, and reduction nature cooling under hydrogen obtains noble metal catalyst behind the high temperature pyrolysis;
(5) noble metal catalyst that step (4) is made impregnated in transition metal salt solution, air-dry heat treatment, and back roasting in Muffle furnace must be used for the composite metal catalyst of microwave degradation dyeing waste water; The carrier quality is 100 with the mass ratio of the rare-earth oxide, noble metal and the transition metal oxide that support in the control composite metal catalyst: (0.2-2.5): (0.1-0.5): (0.3-3.5).
Preferred said rare earth metal salt solutions mass concentration is 1%-8%, the said precious metal salt solution mass concentration of step (3) 0.5%-2%, and soluble transition metal salting liquid mass concentration is 2%-10% described in the step (5).Preferred said rare earth metal solution is: the nitrate solution of lanthanum (La) or cerium (Ce); Described precious metal solution is the chloride salt solution of platinum (Pt) or palladium (Pd); Described transition metal salt solution is the mixed solution of one or more solution of sulfate of nitrate or iron, nickel, copper, zinc or the manganese of iron, nickel, copper, zinc or manganese.General incipient impregnation can obtain needed load capacity.
Heat-treat condition described in preferred above-mentioned steps (2), step (3) and the step (5) is and in baking oven, is warming up to 80-120 ℃, and be 1-3h heat time heating time.
The described roasting heating rate of preferred steps (2) is 5-10 ℃/min, and sintering temperature is 350 ℃-450 ℃, and roasting time is 2-4h; Roasting heating rate described in the step (5) is 5-10 ℃/min, and sintering temperature is 300 ℃-600 ℃, and roasting time is 2-4h; Pyrolysis temperature described in the step (4) is 300 ℃-400 ℃, and the time is 2-4h.
The preliminary treatment of carrier is cleaning, oven dry and roasting; Be specially earlier with under ultrasonic, using the deionized water soaking and washing again after the deionized water clean surface; Again with acid solution soak behind the 8-12h soak ultrasonic cleaning with deionized water after, heat treatment oven dry back roasting.Wherein selecting described ultrasound condition is frequency 20-80kHz, and ultrasonic time is 5-30min; Described acid solution is hydrochloric acid solution or salpeter solution, and the acid solution volumetric concentration is 0.5%-5%; Said heat treatment oven dry is for to be warming up to 80-120 ℃ in baking oven, be 1-3h heat time heating time; Described sintering temperature is 400-600 ℃, and the sintering temperature retention time is 2-4h.Pretreated effect is to remove foreign ion, improves the carrier specific area, improves catalyst stability.
Beneficial effect:
The present invention is a kind of economy, high efficiency preparation method; Add rare earth metal, the catalyst metals activated centre is evenly distributed at carrier surface, have good absorbing property, mechanical strength is high; Transition metal and noble metal mix, and have reduced metal loss.In the microwave catalysis reaction, can promote the generation of hydroxyl radical free radical, promote the degraded of pollutant; This method has economy, efficient, and the stability of a system is good, and is safe, easy to operate, is convenient to advantages such as industry amplification.
Description of drawings
Fig. 1 is the graph of a relation of the made catalyst amounts of instance 1 and dyeing waste water (volume 150ml COD 500mg/L) COD, chroma removal rate; Wherein abscissa is the catalyst addition, the g of unit; Ordinate is a clearance, the % of unit;
Fig. 2 is the graph of a relation that instance 2 made catalyst are reused number of times and dyeing waste water (volume 150ml COD 500mg/L) COD clearance; Wherein abscissa is the catalyst access times, unit; Ordinate is the COD clearance, the % of unit.
The specific embodiment
The specific embodiment below in conjunction with embodiment is done further to specify to foregoing of the present invention again.
Catalyst carrier is the spherical γ type activated alumina of particle diameter 5mm, puts into microwave equipment with behind the deionized water rinsing surface 4 times, under 20kHZ, adds the ultrasonic 30min of deionized water, puts into ultrasonic 5min under the 20kHZ again after adding volumetric concentration 0.5% salt soak 8h.Take out the gamma activity aluminium oxide 120 ℃ put into baking oven baking 1h after, put into Muffle furnace in 500 ℃ of roasting 1.5h activation, subsequent use carrier.
With the carrier incipient impregnation in mass concentration 1% cerous nitrate solution; Put into baking oven behind the natural air drying 30h after 120 ℃ baking 2h cools off down, behind 350 ℃ of following roasting 3h, impregnated in mass concentration 0.5% platinum acid chloride solution, the mixing natural air drying; Behind 105 ℃ of curing 1.5h; Behind 400 ℃ of nitrogen protection roasting 3h, switch to hydrogen reducing and reduce to room temperature naturally, get noble metal catalyst; Noble metal catalyst impregnated in the iron nitrate solution of mass concentration 4%, in 300 ℃ of roasting 2.5h, getting load capacity is 0.28%CeO behind 120 ℃ of baking 1h again
2/ 0.13%Pt/0.55%Fe
2O
3Compound iron platinum catalyst.
As shown in Figure 1; This catalyst applications in the simulation dyeing waste water of COD 500mg/L, in wastewater volume 150ml, pH are 3 simulated wastewater, is added the 3.0ml hydrogen peroxide solution; Put into microwave power 120W; The microwave time microwave device of 15min reacts, and along with the increase of iron platinum catalyst dosage, chroma in waste water and COD clearance is increased gradually.When catalyst amounts was 5.0g, the COD clearance can reach 83%, the rate of discoloring reaches 68%.Show that this catalyst is used for the microwave treatment dyeing waste water and has good treatment effect.
Catalyst carrier is the spherical γ type activated alumina of particle diameter 5mm; Put into microwave equipment with behind the deionized water rinsing surface 4 times; Under 80kHZ, add the ultrasonic 5min of deionized water, add and to take out the gamma activity aluminium oxide behind the volumetric concentration 1.5% salt soak 12h again and add deionized water and put under the 20kHZ behind the ultrasonic 30min, put into baking oven behind 80 ℃ of baking 3h; Put into Muffle furnace in 600 ℃ of roasting 2h activation, get subsequent use carrier.
With the carrier incipient impregnation in mass concentration 8% cerous nitrate solution; Put into baking oven behind the natural air drying 30h after 120 ℃ baking 2h cools off down; Behind 400 ℃ of following roasting 2.5h, impregnated in mass concentration 2% platinum acid chloride solution, the mixing natural air drying is put into 400 ℃ of nitrogen protection roasting 2h behind 80 ℃ of baking 3h; Switch to hydrogen and reduce to the room temperature reduction naturally, get noble metal catalyst; Noble metal catalyst impregnated in the copper-bath of mass concentration 10%, in 600 ℃ of roasting 2h, getting load capacity is 2.24%CeO behind 80 ℃ of baking 3h again
2/ 0.5%Pt/3.5%CuO complex copper platinum catalyst.
As shown in Figure 2; Is in the simulated wastewater of 150ml with this catalyst applications in the COD500mg/L volume, and transferring pH is 3, adds the 3.0ml hydrogen peroxide solution; Put into microwave power 125W; The microwave time, 20min reacted, use copper platinum catalyst microwave treatment simulated wastewater first after, the COD clearance can reach more than 80%.After reusing this catalyst 9 times, the COD clearance still can reach 60%, shows that this catalyst can reuse, and mechanical strength is high, and economic stability is the feasible catalyst that is applicable to the microwave treatment dyeing waste water.
Catalyst carrier is the spherical γ type activated alumina of particle diameter 3mm; Put into microwave equipment with behind the deionized water rinsing surface 3 times; Under 40kHZ, add the ultrasonic 15min of deionized water; Add and put into ultrasonic 10min under the 20kHZ again after volumetric concentration 5% salpeter solution soaks 10h, get the gamma activity aluminium oxide behind 80 ℃ of baking 1.5h, get subsequent use carrier at 400 ℃ of roasting 3h.
Carrier impregnation is put into baking oven after 105 ℃ baking 2h cools off down behind the natural air drying 30h in mass concentration 4% lanthanum nitrate hexahydrate; Behind 450 ℃ of following roasting 2h, impregnated in mass concentration 1% palladium chloride solution; Mixing is air-dry behind 105 ℃ of curing 1h; Behind 300 ℃ of nitrogen protection roasting 4h, hydrogen reducing gets noble metal catalyst.To get noble metal catalyst again and impregnated in mass concentration 2% nickel nitrate solution, in 400 ℃ of roasting 3h, getting load capacity is 1.05%La behind 105 ℃ of baking 1h
2O
3The compound nickel palladium catalyst of/0.42%Pd/0.36%NiO.This catalyst mechanical strength is high, has good absorbing property, is used for the microwave treatment dyeing waste water and is swift in response, and colourity and COD are removed the efficient height.
Claims (8)
1. a catalyst that is used for the microwave degradation dyeing waste water is characterized in that with the activated alumina being carrier, and rare earth metal is for helping catalyst component, and noble metal and transition metal are as active component; Wherein the carrier quality is 100 with the mass ratio of the rare-earth oxide, noble metal and the transition metal oxide that support: (0.2-2.5): (0.1-0.5): (0.3-3.5).
2. one kind prepares the method for catalyst according to claim 1, and its concrete steps are following:
(1) with for use after the carrier preliminary treatment; Described carrier is an activated alumina;
(2) carrier impregnation after the preliminary treatment is gone into rare earth metal salt solutions, roasting in Muffle furnace after mixing, the natural air drying heat treatment;
(3) with the carrier impregnation after the roasting in the step (2) in precious metal salt solution, natural air drying after-baking behind the mixing, the presoma of carried noble metal;
(4) presoma with step (3) carried noble metal places nitrogen atmosphere, and reduction nature cooling under hydrogen obtains noble metal catalyst behind the high temperature pyrolysis;
(5) noble metal catalyst that step (4) is made impregnated in transition metal salt solution, air-dry heat treatment, and back roasting in Muffle furnace must be used for the composite metal catalyst of microwave degradation dyeing waste water; The carrier quality is 100 with the mass ratio of the rare-earth oxide, noble metal and the transition metal oxide that support in the control composite metal catalyst: (0.2-2.5): (0.1-0.5): (0.3-3.5).
3. method according to claim 2; It is characterized in that the rare earth metal salt solutions mass concentration is 1%-8% described in the step (2); The said precious metal salt solution mass concentration of step (3) 0.5%-2%, soluble transition metal salting liquid mass concentration is 2%-10% described in the step (5).
4. method according to claim 2 is characterized in that said rare earth metal solution is: the nitrate solution of lanthanum or cerium; Described precious metal solution is the chloride salt solution of platinum or palladium; Described transition metal salt solution is the mixed solution of one or more solution of sulfate of nitrate or iron, nickel, copper, zinc or the manganese of iron, nickel, copper, zinc or manganese.
5. method according to claim 2 is characterized in that: the heat-treat condition described in said step (2), step (3) and the step (5) is and in baking oven, is warming up to 80-120 ℃, is 1-3h heat time heating time.
6. method according to claim 2 is characterized in that: the described roasting heating rate of step (2) is 5-10 ℃/min, and sintering temperature is 350 ℃-450 ℃, and roasting time is 2-4h; Roasting heating rate described in the step (5) is 5-10 ℃/min, and sintering temperature is 300 ℃-600 ℃, and roasting time is 2-4h; Pyrolysis temperature described in the step (4) is 300 ℃-400 ℃, and the time is 2-4h.
7. method according to claim 2 is characterized in that: the preliminary treatment of carrier is earlier with under ultrasonic, using the deionized water soaking and washing again after the deionized water clean surface; Again with acid solution soak behind the 8-12h soak ultrasonic cleaning with deionized water after, heat treatment oven dry back roasting.
8. method according to claim 7 is characterized in that described ultrasound condition is frequency 20-80kHz, and ultrasonic time is 5-30min; Described acid solution is hydrochloric acid solution or salpeter solution, and the acid solution volumetric concentration is 0.5%-5%; Said heat treatment oven dry is for to be warming up to 80-120 ℃ in baking oven, be 1-3h heat time heating time; Described sintering temperature is 400-600 ℃, and the sintering temperature retention time is 2-4h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012100759450A CN102626639A (en) | 2012-03-21 | 2012-03-21 | Catalyst for microwave degradation of printing and dyeing wastewater and preparation method thereof |
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| CN2012100759450A CN102626639A (en) | 2012-03-21 | 2012-03-21 | Catalyst for microwave degradation of printing and dyeing wastewater and preparation method thereof |
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| CN102626639A true CN102626639A (en) | 2012-08-08 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872896A (en) * | 2012-09-25 | 2013-01-16 | 东南大学 | Catalyst for catalytic oxidation of printing and dyeing wastewater and preparation method for catalyst |
| CN103172138A (en) * | 2013-03-20 | 2013-06-26 | 安洁士石油技术(上海)有限公司 | Preparation method of special microwave sensitizer for oil-field wastewater |
| CN105498740A (en) * | 2016-01-28 | 2016-04-20 | 中国科学院电子学研究所 | Strong microwave absorption catalyst and preparation method and application thereof |
| CN109012740A (en) * | 2018-08-22 | 2018-12-18 | 国家能源投资集团有限责任公司 | Molecular sieve catalyst, preparation method and application for microwave catalysis oxidation processing organic wastewater |
| CN109231711A (en) * | 2018-11-06 | 2019-01-18 | 江苏澳洋生态园林股份有限公司 | A kind of black-odor riverway sewage disposal system and method |
| CN109465009A (en) * | 2018-11-01 | 2019-03-15 | 深圳永清水务有限责任公司 | Catalyst and its preparation method and application for catalytic wet hydrogen peroxide oxidation method |
| CN109701551A (en) * | 2018-12-12 | 2019-05-03 | 佛山科学技术学院 | A kind of loaded catalyst and preparation method thereof, treatment method of printing and dying wastewater |
| CN109876816A (en) * | 2019-02-19 | 2019-06-14 | 江苏海普功能材料有限公司 | A kind of micro ware auxiliary catalysis wet oxidation nanocatalyst and its application |
| CN110818014A (en) * | 2019-07-05 | 2020-02-21 | 天津理工大学 | Bionic removal method of wastewater containing low-concentration organic amine |
| CN114849708A (en) * | 2022-06-10 | 2022-08-05 | 苏州大学 | Three-dimensional macroporous carbon anchored monatomic iron catalyst, and preparation method and application thereof |
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| CN101185888A (en) * | 2007-12-04 | 2008-05-28 | 南京工业大学 | Catalyst for inducing catalytic oxidation process and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872896A (en) * | 2012-09-25 | 2013-01-16 | 东南大学 | Catalyst for catalytic oxidation of printing and dyeing wastewater and preparation method for catalyst |
| CN103172138A (en) * | 2013-03-20 | 2013-06-26 | 安洁士石油技术(上海)有限公司 | Preparation method of special microwave sensitizer for oil-field wastewater |
| CN103172138B (en) * | 2013-03-20 | 2014-04-16 | 安洁士石油技术(上海)有限公司 | Preparation method of special microwave sensitizer for oil-field wastewater |
| CN105498740A (en) * | 2016-01-28 | 2016-04-20 | 中国科学院电子学研究所 | Strong microwave absorption catalyst and preparation method and application thereof |
| CN109012740A (en) * | 2018-08-22 | 2018-12-18 | 国家能源投资集团有限责任公司 | Molecular sieve catalyst, preparation method and application for microwave catalysis oxidation processing organic wastewater |
| CN109465009A (en) * | 2018-11-01 | 2019-03-15 | 深圳永清水务有限责任公司 | Catalyst and its preparation method and application for catalytic wet hydrogen peroxide oxidation method |
| CN109231711A (en) * | 2018-11-06 | 2019-01-18 | 江苏澳洋生态园林股份有限公司 | A kind of black-odor riverway sewage disposal system and method |
| CN109701551A (en) * | 2018-12-12 | 2019-05-03 | 佛山科学技术学院 | A kind of loaded catalyst and preparation method thereof, treatment method of printing and dying wastewater |
| CN109876816A (en) * | 2019-02-19 | 2019-06-14 | 江苏海普功能材料有限公司 | A kind of micro ware auxiliary catalysis wet oxidation nanocatalyst and its application |
| CN110818014A (en) * | 2019-07-05 | 2020-02-21 | 天津理工大学 | Bionic removal method of wastewater containing low-concentration organic amine |
| CN114849708A (en) * | 2022-06-10 | 2022-08-05 | 苏州大学 | Three-dimensional macroporous carbon anchored monatomic iron catalyst, and preparation method and application thereof |
| CN114849708B (en) * | 2022-06-10 | 2023-11-03 | 苏州大学 | Three-dimensional macroporous carbon anchored monoatomic iron catalyst and preparation method and application thereof |
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Application publication date: 20120808 |