CN102008965B - Method for preparing ozone catalytic oxidation catalyst for treating cyanide waste water - Google Patents
Method for preparing ozone catalytic oxidation catalyst for treating cyanide waste water Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052718 tin Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004480 active ingredient Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005096 rolling process Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000006385 ozonation reaction Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 239000011135 tin Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- 238000012423 maintenance Methods 0.000 claims description 5
- 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
- 239000000470 constituent Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 rhodanate Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a method for preparing an ozone catalytic oxidation catalyst for treating cyanide waste water, which is characterized in that amorphous alumina is used as a carrier, and in the process of pelltizing, copper, ferrum and tin which serve as active ingredients are sprayed in form of solution, and are subjected to curing, drying and roasting to prepare a catalyst. The method comprises the following steps of: (a) dissolving metal salts of the copper, the ferrum and the tin into water to form solution; (b) putting the amorphous alumina into a rotating pelletizer, spraying the solution in the step (a) into the pelletizer to perform rolling pelltizing, and controlling the pelltizing diameter; (c) curing the particulate matters obtained in the step (b) for 3 to 24 hours under the condition of water vapor of between 100 and 110 DEG C; and (d) drying and roasting the obtained catalyst in the step (c) to obtain a catalyst serving as a finished product, wherein the drying temperature is between 50 and 180 DEG C, the drying time is between 2 and 10 hours, the roasting temperature is between 400 and 600 DEG C, and the roasting time is between 2 and 8 hours.
Description
Technical field:
The present invention relates to catalyst and make the field, be a kind of catalytic ozonation Preparation of catalysts method of Treatment of Cyanide-containing Wastewater, aim to provide the method for making of simple, with low cost, the eco-friendly highly active catalytic ozonation catalyst of a kind of preparation technology.Catalyst of the present invention is mainly used in the catalytic ozonation method and efficiently removes the organic pollution in the cyanide wastewater.
Background of invention:
Cyanide wastewater is meant the industrial wastewater that contains the CN group.Extract at the non-ferrous metal mineral in the industry production technologies such as gold, silver and bronze, cyanide electroplating, chemical industry, coking, heat treatment and all discharge a large amount of cyanide wastewater; Particularly mineral select the consumption of cyanide in the smelting production technology very big; The CN-mass concentration is higher in the waste water; Also contain compounds such as a large amount of heavy metals, rhodanate, water environment pollution is very serious to external world.
Stipulate among " integrated wastewater discharge standard " GB 8978-1996 of country: the cyanide wastewater mass concentration discharge standard＜0.5mg/L of general enterprise.Although the multiple distinct methods Treatment of Cyanide-containing Wastewater of enterprise's active adoption still has the discharging that exceeds standard of many industrial and mining enterprises.The technical staff still is that environmental management person, enterpriser are striving to find new technology and new method simple to operate, that cost is low, treatment effect is good.
Treatment Methods of Cyanide Wastewater mainly comprises alkaline chlorination process, ferrous sulfate method, hydrogen peroxide method, ozone oxidation method, heating hydrolysis method, electrolysis etc.Wherein, The catalytic ozonation technology is that developed recently gets up a kind ofly degrades at normal temperatures and pressures that those are difficult to by the organic high-level oxidation technology of the independent oxidation of ozone; Can alcohol, ketone, organic acid and the Ester that difficulty is decomposed be continued oxidation Decomposition; More thorough to the organic pollution oxidation, it is high to remove efficient.Aspect wastewater treatment, be widely used at present, obtained removal effect preferably.
The chemical reaction mechanism of ozone Oxidation Treatment cyanide is:
2CN-+2H
++H
2O+3O
3→2H
2CO
3+2O
2+N
2
Ozone generates cyanate with the cyanide reaction earlier, and cyanate produces nitrogen and carbonate after hydrolysis.Adopt the ozone oxidation method to handle the cyanide in the waste water, only need ozone generating apparatus, need not medicament and purchase and transport; And technology is simple, convenient; Processed waste water total cyanide mass concentration can reach national sewage comprehensive emission standard, does not increase other harmful substance, non-secondary pollution in disposing waste liquid; Do not need further processing, the core technology of its process implementing be development and develop that a kind of technology is simple, environmental protection, cheap heterogeneous catalysis.
The patent of Tsing-Hua University [CN1785511A] discloses a kind of Ru/Al
2O
3The catalytic ozonation catalyst adopts equi-volume impregnating with RuCl
3Solution and Al
2O
3The carrier equal-volume mixes, and in shaking table, floods, and obtains finished catalyst through steps such as super-dry, heating using microwaves again.This catalyst all has good effect of removing to aldehydes matter, little molecule acid.But this method selects for use noble metal as active component, and cost is too high, and the mode industrialization of heating using microwave difficulty.Korean Patent [9464043685] has been introduced a kind of multiple transition metal and cellular TiO of catalytic ozonation
2-ZrO
2Catalyst is used for the respond well of deodorizing and sterilization, and shortcoming is that its cellular structure is not suitable for wastewater treatment.The patent [CN1576242A] of Jiahe, Shanghai chemical industry Co., Ltd discloses a kind of paraquat treatment Methods of Cyanide Wastewater; The catalyst that this method is used is the active carbon catalyst series; Can be carrier loaded a certain amount of composite metal elements loaded, this method for preparing catalyst technology is simple.But the liquid after this method Treatment of Cyanide-containing Wastewater can't directly discharge, and needs to get into biochemical treatment system and does further processing, has increased equipment investment cost, and process route is complicated.
Korean Institute of Science and Technology's patent [CN1194626A] has been introduced a kind of hydrogen peroxide, ozone of in the presence of normal temperature and pressure, using and has been done oxidant economy and effectively handle the heterogeneous catalyst that contains various organic pollutant wastewaters.This catalyst comprises and loads on PbO
2, ZrO
2, TiO
2, MgO or their mixture a kind of metal oxide on the element that is selected from Ru, Co, Fe, Cu, Mn, Li and their mixture.This catalyst can reach about 65% to the CODcr clearance of cyanide wastewater 5min; But this catalyst adopts immersion process for preparing; The load of active component inevitably causes the specific area and the pore volume loss of catalyst, has influenced absorption, the catalytic performance of catalyst.Catalyst preparation process is complicated simultaneously, and the choice of powder metal oxide is a carrier, and difficulty is amplified in industrialization.
Summary of the invention:
Technical problem to be solved by this invention is: a kind of bigger serface Preparation of catalysts method that catalytic ozonation is removed the cyanide wastewater organic pollution that is used for is provided.Method for preparing catalyst of the present invention is simple, and environmental friendliness is with low cost; This catalyst is a kind of highly active heterogeneous catalytic ozonation catalyst, has overcome existing catalyst preparation process complicacy, has been difficult to shortcomings such as industrialization amplification, cost height; And catalytic activity is higher, and the cyanide wastewater after the processing need not to carry out other processing again, can directly discharge.
The present invention is a kind of catalytic ozonation Preparation of catalysts method of Treatment of Cyanide-containing Wastewater, it is characterized in that:
With the amorphous alumina is carrier powder, in the rolling granulation process, active ingredient copper, iron, tin is sprayed into the form of solution, through processing finished catalyst after granulation, maintenance, oven dry, the roasting.This catalyst is mainly used in the removal of the organic pollution of the difficult degradation in the cyanide wastewater.Specifically comprise following step:
(a) with the slaine of active ingredient copper, iron, the tin wiring solution-forming that is dissolved in water;
(b) amorphous alumina is put into the rotation comminutor, the solution that step (a) is obtained sprays into the granulation of rolling, and the diameter of control granulation is 1～8mm;
(c) the particle maintenance under 100～110 ℃ water vapour condition that step (b) is obtained, curing time 3～24 hours;
(d) catalyst that step (c) is obtained obtains finished catalyst through oven dry, roasting.The bake out temperature of catalyst is 50～180 ℃, and be 2～10 hours drying time, and sintering temperature is 400～600 ℃, and roasting time is 2～8 hours.
Described amorphous alumina is made through the high temperature fast dewatering by industrial aluminium hydroxide, and its specific area is 150～350m
2/ g, total pore volume 0.20～0.45ml/g, particle mean size l～80 μ m.
Described active ingredient copper, iron are with the form of nitrate, and tin adds the water wiring solution-forming with muriatic form, and the solution straying quatity is 2～50% of an amorphous alumina gross mass.
The load capacity of described active constituent copper, iron, tin is 0.1～20.0wt% of amorphous alumina gross mass.
According to preparation method of the present invention, it is characterized in that:
The bake out temperature of catalyst is 90～160 ℃ in the step, and be 4～8 hours drying time, and sintering temperature is 450～550 ℃, and roasting time is 4～6 hours.
Described active ingredient copper, iron are with the form of nitrate, and tin adds the water wiring solution-forming with muriatic form, and the solution straying quatity is 4～48% of an amorphous alumina gross mass.
The load capacity of described active constituent copper, iron, tin is 0.5～10wt% of amorphous alumina gross mass.
Can be used for the catalytic ozonation reaction of the removal of organic pollution in the various wastewater with the catalyst of the inventive method production.According to the present invention, be specially adapted to the efficient removal of organic pollution in the cyanide wastewater by the catalyst of this method production.
Only with 3 processing steps fast and the economic catalyst that is used for efficiently removing the cyanide wastewater organic pollution of producing, preparation process is simple for technology of the present invention, and suitability for industrialized is amplified, and pollution-free, economic environmental protection.
Because this catalyst activity component particles particle diameter is little, be evenly distributed, and specific area and the pore volume of preparation catalyst are bigger, have better absorption, catalytic performance, so catalyst of the present invention has high activity.
The specific embodiment:
Embodiment 1
Get 226gCu (NO
3)
23H
2O, 379gFe (NO
3)
39H
2O, 174gSnCl
45H
2O adds 1.5kg water, wiring solution-forming.Get 5.4kg amorphous alumina (CNOOC Tianjin Chemical Research & Desing Inst produce, trade names AKF101), spray into the solution that the prepares granulation of rolling and stop during to particle diameter 3mm; At 101 ℃ of following maintenance 20hr; 110 ℃ of dry 4hr, 550 ℃ of roasting 3hr obtain the catalytic ozonation catalyst.The specific area and the active component content of catalyst finished product are listed in table 1.
Catalyst performance evaluation is through realizing with lower device:
Reactor: fixed bed reactors
Loaded catalyst: 100ml, the filling ratio of height to diameter is 4: 1
Temperature: normal temperature
The time of staying: 20min
Ozone generating capacity: 4.5g/hr
Wastewater source: be selected from certain acrylonitrile plant waste water, get into the preceding import CODcr value of device for catalyzing and oxidating ozone: 180～200mg/L, import CN
-Concentration: 35～50mg/L.
The evaluation result of catalyst is seen table 2 and table 3.
Embodiment 2
The configuration selection of active component solution is equivalent to the copper nitrate of amorphous alumina carrier quality 0.5%, ferric nitrate, and stannic chloride, all the other catalyst preparation step are with embodiment 1.The specific area and the active component content of catalyst finished product are listed in table 1.
This catalyst is to test like the method among the embodiment 1, and the evaluation result of its catalyst is seen table 2 and table 3.
Embodiment 3:
The configuration selection of active component solution is equivalent to the copper nitrate of amorphous alumina carrier quality 3.0%, ferric nitrate, and stannic chloride, all the other catalyst preparation step are with embodiment 1.The specific area and the active component content of catalyst finished product are listed in table 1.
This catalyst is to test like the method among the embodiment 1, and the evaluation result of its catalyst is seen table 2 and table 3.
Embodiment 4:
The granulation of rolling in the catalyst preparation process stops when particle diameter 5mm, and all the other catalyst preparation step are with embodiment 1.The specific area and the active component content of catalyst finished product are listed in table 1.
This catalyst is to test like the method among the embodiment 1, and the evaluation result of its catalyst is seen table 2 and table 3.
Comparative example 1:
Get 226gCu (NO
3)
23H
2O, 379gFe (NO
3)
39H
2O, 174gSnCl
45H
2O adds water and is made into 3L solution, get the 5kg alumina support (diameter 3～5mm), with above-mentioned maceration extract incipient impregnation to carrier, 110 ℃ of dry 4hr, 550 ℃ of roasting 3hr obtain the catalytic ozonation catalyst.The specific area and the active component content of catalyst finished product are listed in table 1.
This catalyst is to test like the method among the embodiment 1, and the evaluation result of its catalyst is seen table 2 and table 3.
Comparative example 2:
The configuration selection of active component solution is equivalent to the copper nitrate of amorphous alumina carrier quality 3.0%, ferric nitrate, and stannic chloride, all the other catalyst preparation step are with comparative example 1.The specific area and the active component content of catalyst finished product are listed in table 1.
This catalyst is to test like the method among the embodiment 1, and the evaluation result of its catalyst is seen table 2 and table 3.
The specific area of table 1 catalyst and active component content
CODcr data contrast before and after table 2 wastewater treatment
CN before and after table 3 wastewater treatment
-The concentration contrast
Claims (2)
1. the catalytic ozonation Preparation of catalysts method of a Treatment of Cyanide-containing Wastewater is characterized in that:
With the amorphous alumina is carrier powder; In the rolling granulation process; Active ingredient copper, iron, tin are sprayed into the form of solution, and through processing finished catalyst after granulation, maintenance, oven dry, the roasting, this catalyst is mainly used in the catalytic oxidation of the organic pollution of the difficult degradation in the cyanide wastewater; Specifically comprise following step:
(a) with the slaine of active ingredient copper, iron, the tin wiring solution-forming that is dissolved in water;
(b) amorphous alumina is put into the rotation comminutor, the solution that step (a) is obtained sprays into the granulation of rolling, and the diameter of control granulation is 1～8mm;
(c) the particle maintenance under 100～110 ℃ water vapour condition that step (b) is obtained, curing time 3～24 hours;
(d) catalyst that step (c) is obtained obtains finished catalyst through oven dry, roasting; The bake out temperature of catalyst is 50～180 ℃, and be 2～10 hours drying time, and sintering temperature is 400～600 ℃, and roasting time is 2～8 hours;
Described amorphous alumina is made through the high temperature fast dewatering by industrial aluminium hydroxide, and its specific area is 150～350m2/g, total pore volume 0.20～0.45ml/g, particle mean size 1～80 μ m;
Described active ingredient copper, iron are with the form of nitrate, and tin adds the water wiring solution-forming with muriatic form, and the solution straying quatity is 2～50% of an amorphous alumina gross mass;
The load capacity of described active constituent copper, iron, tin is 0.1～20.0wt% of amorphous alumina gross mass.
2. according to this claim 1 described preparation method, it is characterized in that:
The bake out temperature of catalyst is 90～160 ℃ in the step, and be 4～8 hours drying time, and sintering temperature is 450～550 ℃, and roasting time is 4～6 hours;
Described active ingredient copper, iron are with the form of nitrate, and tin adds the water wiring solution-forming with muriatic form, and the solution straying quatity is 4～48% of an amorphous alumina gross mass;
The load capacity of described active constituent copper, iron, tin is 0.5～10wt% of amorphous alumina gross mass.
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|---|---|---|---|
| CN201010539704A CN102008965B (en) | 2010-11-09 | 2010-11-09 | Method for preparing ozone catalytic oxidation catalyst for treating cyanide waste water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010539704A CN102008965B (en) | 2010-11-09 | 2010-11-09 | Method for preparing ozone catalytic oxidation catalyst for treating cyanide waste water |
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| CN104108782B (en) * | 2014-03-03 | 2016-04-20 | 福建省双旗山矿业有限责任公司 | Ozone is except cyanogen process |
| CN104069860B (en) * | 2014-06-27 | 2016-07-27 | 北京林业大学 | The preparation of magnetic nano copper ferrum oxyhydroxide and the application in O3 catalytic oxidation depollution thereof |
| CN106881088A (en) * | 2015-12-15 | 2017-06-23 | 南京源泉环保科技股份有限公司 | A kind of air oxidation broken cyanide catalyst and preparation method thereof |
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| CN112452338A (en) * | 2020-12-24 | 2021-03-09 | 江苏治水有数环保科技有限公司 | Ozone catalytic oxidation catalyst for advanced treatment of badan pesticide wastewater and preparation method thereof |
| CN114602494B (en) * | 2022-05-12 | 2022-07-29 | 中国环境科学研究院 | A method for preparing multi-metal ozone catalyst by blending-impregnation combined method |
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| CN1785507A (en) * | 2005-11-22 | 2006-06-14 | 天津化工研究设计院 | Ozone decomposition catalyst and its preparation method |
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