CN101584988A - Bi-component composite type metallic catalyst and application thereof - Google Patents
Bi-component composite type metallic catalyst and application thereof Download PDFInfo
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- CN101584988A CN101584988A CNA2009100970666A CN200910097066A CN101584988A CN 101584988 A CN101584988 A CN 101584988A CN A2009100970666 A CNA2009100970666 A CN A2009100970666A CN 200910097066 A CN200910097066 A CN 200910097066A CN 101584988 A CN101584988 A CN 101584988A
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- composite type
- metallic catalyst
- type metallic
- component composite
- acetophenone
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- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000003863 metallic catalyst Substances 0.000 title claims abstract description 29
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000002803 maceration Methods 0.000 claims description 13
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 13
- 206010013786 Dry skin Diseases 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 39
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006385 ozonation reaction Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 aromatic ketone compound Chemical class 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- ORFSSYGWXNGVFB-UHFFFAOYSA-N sodium 4-amino-6-[[4-[4-[(8-amino-1-hydroxy-5,7-disulfonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound COC1=C(C=CC(=C1)C2=CC(=C(C=C2)N=NC3=C(C4=C(C=C3)C(=CC(=C4N)S(=O)(=O)O)S(=O)(=O)O)O)OC)N=NC5=C(C6=C(C=C5)C(=CC(=C6N)S(=O)(=O)O)S(=O)(=O)O)O.[Na+] ORFSSYGWXNGVFB-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Abstract
The invention discloses a bi-component composite type metallic catalyst and application thereof, the bi-component composite type metallic catalyst comprises a carrier and active components loaded on the carrier. The carrier is active aluminum oxide, the active components are cupric oxide and ruthenium. Compared to the prior art, the preparation of the bi-component composite type metallic catalyst prepared by the invention is simple, though a small amount of precious metals are doped, the catalytic activity of the catalyst can be improved greatly, the costs are low, the activity is good, the application prospect is good. The bi-component composite type metallic catalyst provided by the invention can be used for removing acetophenone in the water by catalytic ozonation, the efficiency of removing acetophenone by ozone can be improved greatly, and the ozone utilization ratio can be improved.
Description
(1) technical field
The present invention relates to a kind of bi-component composite type metallic catalyst and application thereof, especially remove the application in the acetophenone in the water in O3 catalytic oxidation.
(2) background technology
In recent years, along with developing rapidly of industry, the waste water that discharged of industry has also presented the characteristics of complicated componentization, produced a large amount of new, can not be by organic pollution biochemical degradation, poisonous and hazardous, general processing method is difficult to administer.
Ozone is as a kind of strong oxidizer of cleaning, it has obtained using widely in the processing of drinking water and trade effluent, but the oxidation of ozone has certain selectivity, oxidation operation is thorough inadequately. at above deficiency, in recent years, develop high-level oxidation technology, promptly in processing procedure, impelled ozone to decompose the strong oxidizer OH that produces efficiently a kind of and non-selectivity.At present, such technology mainly contains following several form: (1) O
3/ H
2O
2(2) O
3/ UV; (3) O
3/ ultrasonic wave; (4) O
3/ metal ion; (5) O
3/ solid catalyst (below be designated as O
3/ M) etc.
In above-mentioned several technologies, O
3/ M has been subjected to people's favor with its unique advantage, advantage is as follows:
1) degradation efficiency height, the removal of organic pollution is more thorough
2) solid catalyst easily separates with water body, realizes the recovery and the regeneration of catalyst easily
3) this technology is insensitive to the effect of free radical quencher
4) reaction is carried out at normal temperatures and pressures
5) heterocatalysis technology has obtained using comparatively widely in chemical industry
The metal catalytic ozonisation is a kind of oxidation technology that grew up in the last few years, though it has showed very high efficient to organic removal in the water, and efficient catalytic ozonisation Study of Catalyst is the core and the difficult point of metal catalytic ozonisation technology.In heterogeneous catalysis ozonisation technology, the catalyst of research concentrates on the transition metal oxide, as MnO mostly
2, TiO
2, Co
3O
4Deng.About this respect, relevant report has [Li Xin, " material science and technology " are used for the copper catalyst preparation and the performance study of water treatment procedure, 2007,6:313-315], [Ma Jun, " Chinese water supply and drainage ", MnO
X/ GAC heterogeneous catalysis ozone oxidation degradation of organic substances mechanism is inquired into, and 2007,4:106-108] etc.There are some researches show, noble metal can effectively improve the oxidation efficiency of some oxidation systems, as Lin etc. the catalytic activity of finding noble metal in the research of different catalysts catalytic decomposition liquid phase ozone apparently higher than burning, in the CWO system, mineral carbon load noble metal Ru catalyst has good catalytic activity, but fancy price has limited its application in actual production.
At present, few to the research report of the compound catalyst of common metal and noble metal in the metal catalytic ozonisation catalyst both at home and abroad.In the present invention, the common metal oxide combined with noble metal has prepared bi-component composite type metallic catalyst, has not only reduced the cost of manufacture of catalyst, has also improved the catalytic activity of catalyst greatly, has higher utility.
Acetophenone is a kind of important aromatic ketone compound, be important industrial chemicals and the intermediate in pharmaceuticals industry, plastics industry, perfume industry and other organic synthesis processes, also be the accessory substance that the ethylbenzene catalytic oxidation is produced styrene, in its waste water that extensively is present in Fine Chemical Works and is discharged.The degradation efficiency of the independent ozonisation of acetophenone is extremely low, and therefore, how effectively improving ozone degradation acetophenone efficient is a problem that is worth research.
(3) summary of the invention
The primary technical problem that the present invention will solve is to provide a kind of bi-component composite type metallic catalyst, and this Catalyst Production cost is low, and the catalytic activity height has higher using value.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of bi-component composite type metallic catalyst comprises carrier and the active component that is carried on the carrier, and described carrier is active alundum (Al, and described active component is cupric oxide and ruthenium, is designated as CuO-Ru/Al
2O
3Described bi-component composite type metallic catalyst prepares according to following steps:
1) with Gerhardite Cu (NO
3)
23H
2O, hydrate ruthenium trichloride RuCl
33H
2O is dissolved in and is made into maceration extract in the water; Based on described Gerhardite CuNO
33H
2O and hydrate ruthenium trichloride RuCl
33H
2O, described Gerhardite Cu (NO
3)
23H
2O and hydrate ruthenium trichloride RuCl
33H
2The weight proportion of O is as follows: Cu (NO
3)
23H
2O97.9%～99.4%, RuCl
33H
2O 0.6%～2.1%; Copper nitrate Cu (NO in the control maceration extract
3)
2With ruthenium trichloride RuCl
3Total mass concentration be 365～422g/L;
2) adopt equi-volume impregnating, with the active alundum (Al of carrier pour into step 1) join maceration extract in dipping fully;
3) with step 2) macerate that obtains is 80～100 ℃ of dryings 2～4 hours;
4) carrier that dried load is had the active component presoma promptly gets described bi-component composite type metallic catalyst CuO-Ru/Al 430～470 ℃ of roastings 10～13 hours
2O
3
The Gerhardite that the present invention uses contains 3 crystallizations water for analyzing the pure blue crystal, and content is not less than 99.0%.
The hydrate ruthenium trichloride that the present invention uses is top grade black brown crystal, and Ru content is 38.2%, and chlorinity is 39.5%.
The active alundum (Al that the present invention uses is for white or slightly other tones spherical, and diameter d is about 3.5mm～5mm, and compression strength is greater than 50.0, and bulk density is less than 0.96.
The CuO-Ru/Al that makes according to the inventive method
2O
3The catalyst outward appearance is jade-green active alundum (Al spheroid, and diameter d is about 3.5mm～5mm, and density is about 150.7g/cm
3
The present invention is in step 2) in adopt equi-volume impregnating to flood, so-called " equi-volume impregnating " is about to carrier and can absorbs volume with it and flood liquid phase accordingly and mix, and reaches complete moistening state.As long as mix with drying after, active component can be evenly distributed on the carrier surface, can save to filter and mother liquor reclaims and ly tires out.Those skilled in the art can be according to selected carrier, and test can determine to use the maceration extract of how many volumes through limited number of time.For the bigger catalyst of load capacity,, can come to achieve the goal with repeatedly flooding step by step if, once can not meet the demands because solubility is limit.As carrier, the volumetric usage of maceration extract is generally 1.60-1.88ml/g in the quality of active alundum (Al with active alundum (Al in the present invention, and dip time is generally at 4-5 hour.
Further, maceration extract of the present invention is based on described Gerhardite CuNO
33H
2O and hydrate ruthenium trichloride RuCl
33H
2O, the weight proportion of each solute material composition is preferably: Cu (NO
3)
23H
2O 99.0%, RuCl
33H
2O 1.0%; Copper nitrate Cu (NO in the maceration extract
3)
2With ruthenium trichloride RuCl
3Total mass concentration be preferably 392g/L;
The drying condition of described step 3) was preferably: 90 ℃ of dryings 3 hours.
The roasting condition of described step 4) was preferably: 450 ℃ of roastings 12 hours.
Second technical problem that the present invention will solve is to provide the application of a kind of bi-component composite type metallic catalyst of the present invention acetophenone in O3 catalytic oxidation water, to improve the clearance of organic pollutant acetophenone in the water, reduce the COD of water sample, improve the utilization ratio of ozone.
The present invention is used for O3 catalytic oxidation water acetophenone with described bi-component composite type metallic catalyst, the process conditions of acetophenone are specifically carried out according to following in the described O3 catalytic oxidation water: regulate the pH value of water solution that contains acetophenone and arrive 2.5-5, the dosage of controlling described bi-component composite type metallic catalyst is 5～30g/L, feed the ozone degradation acetophenone, the input amount of ozone is 25～75mgmin
-1The pH value of water solution that contains acetophenone is under greater than 5 situation, and acetophenone still can be degraded fast, but compares with independent ozonisation, and efficient has only improved 20%, does not possess too remarkable advantages.Bi-component composite type metallic catalyst of the present invention is applicable to the removal of acetophenone in the aqueous solution that contains acetophenone of concentration 0-400ppm, when handling the degraded fully that the sufficiently long time can realize acetophenone.
Compared with prior art, the prepared bi-component composite type metallic catalyst of the present invention has the following advantages:
A) make simply, and only mixed up the catalytic activity that a spot of noble metal has just improved catalyst greatly, cost is low, and active good, application prospect is splendid.
B) bi-component composite type metallic catalyst of the present invention effectively O3 catalytic oxidation remove acetophenone, improve the efficient that ozone is removed acetophenone greatly, improved the utilization rate of ozone.
(4) description of drawings
Fig. 1 is the Experimental equipment of acetophenone in the ozone oxidation degradation water of the present invention.
(5) specific embodiment
With instantiation technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto.
Embodiment 1
Take by weighing the solution of the hydrate ruthenium trichloride 150ml of being made into soluble in water of the Gerhardite of 70g and 1.5g, while stir active alumina carrier (Chemical Reagent Co., Ltd., Sinopharm Group, 20001661) equivalent infuse then with 80g.Flood after five hours the macerate that will obtain 80 ℃ of dryings 2 hours.With the 430 ℃ of roastings 10 hours in muffle furnace of above-mentioned dry thing, obtain the catalyst finished product then.CuO-Ru/Al
2O
3The catalyst outward appearance is green active alundum (Al spheroid, and diameter d is about 3.5mm～5mm, and density is about 150.9g/cm
3
Take by weighing the solution of the Gerhardite 150ml of being made into soluble in water of 70g, while stir active alumina carrier (Chemical Reagent Co., Ltd., Sinopharm Group, 20001661) equivalent infuse then with 80g.Flood after five hours the macerate that will obtain 80 ℃ of dryings 2 hours.With the 430 ℃ of roastings 10 hours in muffle furnace of above-mentioned dry thing, obtain the catalyst finished product then.CuO/Al
2O
3The catalyst outward appearance is yellowish green active alundum (Al spheroid.
The said goods is used for the solution (acetophenone concentration is 200ppm) for preparing with acetophenone.With sulfuric acid the pH value of solution value is transferred to about 2.5.The dosage of catalyst is 10g/L.Half batch processing experiment is adopted in experiment, and experiment is 71mgmin at ozone output
-1Carry out under the condition.The experimental technique flow chart is seen Fig. 1.
Effect as a comparison under same experimental conditions, has been made simultaneously of above-mentioned and has not been mixed the Catalysts Cu O/Al that ruthenium trichloride makes
2O
3O3 catalytic oxidation is the result compare.
Detection method: the pH pH-value determination pH adopts the acidity assaying instrument; The concentration of acetophenone adopts high performance liquid chromatograph Waters 1525-2996 (U.S.) to measure chromatographic column: Symmetry C18 post (5um); Phase flows: methanol (v/v)=80/20, flow velocity are 1.0mLmin
-1COD measures and adopts potassium dichromate method (GB/T11914--1989 " the mensuration dichromate titration of hydrochemistry oxygen demand ").
Effect such as table 1 behind the water sample processing 30min:
Table 1
Take by weighing the solution of the hydrate ruthenium trichloride 150ml of being made into soluble in water of the Gerhardite of 75g and 0.75g, while stir active alumina carrier (Chemical Reagent Co., Ltd., Sinopharm Group, 20001661) equivalent infuse then with 80g.Flood after five hours the macerate that will obtain 90 ℃ of dryings 3 hours.With the 450 ℃ of roastings 12 hours in muffle furnace of above-mentioned dry thing, obtain the catalyst finished product then.CuO-Ru/Al
2O
3The catalyst outward appearance is green active alundum (Al spheroid, and diameter d is about 3.5mm～5mm, and density is about 150.6g/cm
3
Take by weighing the solution of the Gerhardite 150ml of being made into soluble in water of 75g, while stir active alumina carrier (Chemical Reagent Co., Ltd., Sinopharm Group, 20001661) equivalent infuse then with 80g.Flood after five hours the macerate that will obtain 90 ℃ of dryings 3 hours.With the 450 ℃ of roastings 12 hours in muffle furnace of above-mentioned dry thing, obtain the catalyst finished product then.CuO/Al
2O
3The catalyst outward appearance is yellowish green active alundum (Al spheroid.
The said goods is used for the solution (acetophenone concentration is 200ppm) for preparing with acetophenone.With sulfuric acid the pH value of solution value is transferred to about 5.0.The dosage of catalyst is 10g/L.Half batch processing experiment is adopted in experiment, and experiment is 71mgmin at ozone output
-1Carry out under the condition.The experimental technique flow chart is seen Fig. 1.
Effect as a comparison under same experimental conditions, has been made simultaneously of above-mentioned and has not been mixed the Catalysts Cu O/AL that ruthenium trichloride makes
2O
3O3 catalytic oxidation is the result compare.
Detection method: the pH pH-value determination pH adopts the acidity assaying instrument; The concentration of acetophenone adopts high performance liquid chromatograph Waters 1525-2996 (U.S.) to measure chromatographic column: Symmetry C18 post (5um); Phase flows: methanol (v/v)=80/20, flow velocity are 1.0mLmin
-1COD measures and adopts potassium dichromate method (GB/T11914--1989 " the mensuration dichromate titration of hydrochemistry oxygen demand ").
Effect such as table 1 behind the water sample processing 30min:
Table 1
Embodiment 3
Take by weighing the solution of the hydrate ruthenium trichloride 150ml of being made into soluble in water of the Gerhardite of 80g and 0.5g, while stir active alumina carrier (Chemical Reagent Co., Ltd., Sinopharm Group, 20001661) equivalent infuse then with 80g.Flood after five hours the macerate that will obtain 100 ℃ of dryings 4 hours.With the 470 ℃ of roastings 13 hours in muffle furnace of above-mentioned dry thing, obtain the catalyst finished product then.CuO-Ru/Al
2O
3The catalyst outward appearance is green active alundum (Al spheroid, and diameter d is about 3.5mm～5mm, and density is about 150.2g/cm
3
Take by weighing the solution of the Gerhardite 150ml of being made into soluble in water of 80g, while stir active alumina carrier (Chemical Reagent Co., Ltd., Sinopharm Group, 20001661) equivalent infuse then with 80g.Flood after five hours the macerate that will obtain 100 ℃ of dryings 4 hours.With the 470 ℃ of roastings 13 hours in muffle furnace of above-mentioned dry thing, obtain the catalyst finished product then.CuO/Al
2O
3The catalyst outward appearance is yellowish green active alundum (Al spheroid.
The said goods is used for the solution (acetophenone concentration is 200ppm) for preparing with acetophenone.With sulfuric acid the pH value of solution value is transferred to about 5.0.The dosage of catalyst is 10g/L.Half batch processing experiment is adopted in experiment, and experiment is 71mgmin at ozone output
-1Carry out under the condition.The experimental technique flow chart is seen Fig. 1.
Effect as a comparison under same experimental conditions, has been made simultaneously of above-mentioned and has not been mixed the Catalysts Cu O/Al that ruthenium trichloride makes
2O
3O3 catalytic oxidation is the result compare.
Detection method: the pH pH-value determination pH adopts the acidity assaying instrument; The concentration of acetophenone adopts high performance liquid chromatograph Waters 1525-2996 (U.S.) to measure chromatographic column: Symmetry C18 post (5um); Phase flows: methanol (v/v)=80/20, flow velocity are 1.0mLmin
-1COD measures and adopts potassium dichromate method (GB/T11914--1989 " the mensuration dichromate titration of hydrochemistry oxygen demand ").
Effect such as table 1 behind the water sample processing 30min:
Table 1
Embodiment 4
Take by weighing the solution of the hydrate ruthenium trichloride 150ml of being made into soluble in water of the Gerhardite of 75g and 0.75g, while stir active alumina carrier (Chemical Reagent Co., Ltd., Sinopharm Group, 20001661) equivalent infuse then with 80g.Flood after five hours the macerate that will obtain 90 ℃ of dryings 3 hours.With the 450 ℃ of roastings 12 hours in muffle furnace of above-mentioned dry thing, obtain the catalyst finished product then.CuO-Ru/Al
2O
3The catalyst outward appearance is jade-green active alundum (Al spheroid, and diameter d is about 3.5mm～5mm, and density is about 150.6g/cm
3
Take by weighing the solution of the copper nitrate 150ml of being made into soluble in water of 75g, while stir active alumina carrier (Chemical Reagent Co., Ltd., Sinopharm Group, 20001661) equivalent infuse then with 80g.Flood after five hours the macerate that will obtain 90 ℃ of dryings 3 hours.With the 450 ℃ of roastings 12 hours in muffle furnace of above-mentioned dry thing, obtain the catalyst finished product then.CuO/Al
2O
3The catalyst outward appearance is yellowish green active alundum (Al spheroid.
The said goods is used for the mixed solution (acetophenone and concentration of oxalic acid are respectively 100ppm) for preparing with acetophenone and oxalic acid.With sulfuric acid the pH value of solution value is transferred to about 3.0.The dosage of catalyst is 10g/L.Half batch processing experiment is adopted in experiment, the experimental technique flow chart Fig. 1 that sees Appendix.
Effect as a comparison under same experimental conditions, has been made simultaneously of above-mentioned and has not been mixed the Catalysts Cu O/Al that ruthenium trichloride makes
2O
3O3 catalytic oxidation is the result compare.
Detection method: the pH pH-value determination pH adopts the acidity assaying instrument; The concentration of acetophenone adopts high performance liquid chromatograph Waters 1525-2996 (U.S.) to measure chromatographic column: Symmetry C18 post (5um); Phase flows: methanol (v/v)=80/20, flow velocity are 1.0mLmin
-1The concentration of oxalic acid adopts the ICS1500 ion chromatography.
Effect such as table 3 behind the water sample processing 30min:
Table 3
Claims (9)
1, a kind of bi-component composite type metallic catalyst comprises carrier and the active component that is carried on the carrier, and described carrier is active alundum (Al, and described active component is cupric oxide and ruthenium; Described bi-component composite type metallic catalyst prepares according to following steps:
1) with Gerhardite CuNO
33H
2O, hydrate ruthenium trichloride RuCl
33H
2O is dissolved in and is made into maceration extract in the water; Based on described Gerhardite CuNO
33H
2O and hydrate ruthenium trichloride RuCl
33H
2O, described Gerhardite Cu (NO
3)
23H
2O and hydrate ruthenium trichloride RuCl
33H
2The weight proportion of O is as follows: Cu (NO
3)
23H
2O 97.9%～99.4%, RuCl
33H
2O 0.6%～2.1%; Copper nitrate Cu (NO in the control maceration extract
3)
2With ruthenium trichloride RuCl
3Total mass concentration be 365～422g/L;
2) adopt equi-volume impregnating, with the active alundum (Al of carrier pour into step 1) join maceration extract in dipping fully;
3) with step 2) macerate that obtains is 80～100 ℃ of dryings 2～4 hours;
4) carrier that dried load is had the active component presoma promptly gets described bi-component composite type metallic catalyst 430～470 ℃ of roastings 10～13 hours.
2, bi-component composite type metallic catalyst as claimed in claim 1 is characterized in that described active alundum (Al is spherical, and diameter d is 3.5mm～5mm, and compression strength is greater than 50.0, and bulk density is less than 0.96.
3, bi-component composite type metallic catalyst as claimed in claim 2 is characterized in that described step 2) in, the volume of maceration extract is counted 1.60～1.88ml/g with the quality of active alundum (Al.
4, bi-component composite type metallic catalyst as claimed in claim 3 is characterized in that described step 2) in dip time be 4～5 hours.
5,, it is characterized in that described maceration extract is based on described Gerhardite CuNO as the described bi-component composite type metallic catalyst of one of claim 1～4
33H
2O and hydrate ruthenium trichloride RuCl
33H
2O, the weight proportion of each solute material composition is: Cu (NO
3)
23H
2O99.0%, RuCl
33H
2O 1.0%; Copper nitrate Cu (NO in the maceration extract
3)
2With ruthenium trichloride RuCl
3Total mass concentration be 392g/L.
6, as the described bi-component composite type metallic catalyst of one of claim 1～4, it is characterized in that the drying condition of described step 3) is: 90 ℃ of dryings 3 hours.
7,, it is characterized in that the roasting condition of described step 4) is: 450 ℃ of roastings 12 hours as the described bi-component composite type metallic catalyst of one of claim 1～4.
8, the application of bi-component composite type metallic catalyst as claimed in claim 1 acetophenone in O3 catalytic oxidation water.
9, application as claimed in claim 8, it is characterized in that acetophenone carries out according to following in the described O3 catalytic oxidation water: regulate pH value of water solution to 2.5～5 of containing acetophenone, the dosage of controlling described bi-component composite type metallic catalyst is 5～30g/L, feed the ozone degradation acetophenone, the input amount of ozone is 25～75mgmin
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